CA1111177A - Impact modified polymer composition - Google Patents
Impact modified polymer compositionInfo
- Publication number
- CA1111177A CA1111177A CA321,405A CA321405A CA1111177A CA 1111177 A CA1111177 A CA 1111177A CA 321405 A CA321405 A CA 321405A CA 1111177 A CA1111177 A CA 1111177A
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- Canada
- Prior art keywords
- modifier
- composition
- block copolymer
- cpvc
- impact
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L27/24—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
Abstract
ABSTRACT OF THE DISCLOSURE
Chlorinated polyvinyl chloride resin (CPCV) is blended with a block copolymer of styrene and a diene (SD) or of styrene-diene-styrene (SDS), which block copolymer is referred to as a "pro-modifier" because, by itself, it performs a dual function of processing aid and impact modi-fier in CPVC. For tailoring specific desirable impact properties and physical characteristics into a CPVC resin composition, it may be desirable to use a conventional impact modifier in combination with the block copolymer.
When the block copolymer is used, such use being referred to as that of a "co-modifier", the block copolymer and con-ventional impact modifier provide a CPVC composition with unexpectedly enhanced impact strength. The block copolymer consists essentially of a vinyl aromatic compound and a conjugated diene such as styrene-diene (SD) diblock co-polymer, or a styrene-diene-styrene (SDS) polyblock copolymer having a linear or radial block structure or mixtures of linear and radial block copolymers. When a conventional impact modifier is used, it may be any elasto-mer additive, preferably a nucleated rubbery graft copoly-mer, but a minor quantity by weight of a synthetic resinous interpolymer which contains no rubber polymer, may also be used.
Chlorinated polyvinyl chloride resin (CPCV) is blended with a block copolymer of styrene and a diene (SD) or of styrene-diene-styrene (SDS), which block copolymer is referred to as a "pro-modifier" because, by itself, it performs a dual function of processing aid and impact modi-fier in CPVC. For tailoring specific desirable impact properties and physical characteristics into a CPVC resin composition, it may be desirable to use a conventional impact modifier in combination with the block copolymer.
When the block copolymer is used, such use being referred to as that of a "co-modifier", the block copolymer and con-ventional impact modifier provide a CPVC composition with unexpectedly enhanced impact strength. The block copolymer consists essentially of a vinyl aromatic compound and a conjugated diene such as styrene-diene (SD) diblock co-polymer, or a styrene-diene-styrene (SDS) polyblock copolymer having a linear or radial block structure or mixtures of linear and radial block copolymers. When a conventional impact modifier is used, it may be any elasto-mer additive, preferably a nucleated rubbery graft copoly-mer, but a minor quantity by weight of a synthetic resinous interpolymer which contains no rubber polymer, may also be used.
Description
1~11177 IMPACT MODIFIED POLYMER COMPOSITION
Background of the Invention It is well known that a chlorinated vinyl polymer referred to as chlorinated polyvinyl chloride (CPVC) has excellent high temperature performance5 characteristics, among other desirable physical properties. CPVC resin is commercially available as a mixed polymeric structure of vinyl chloride, vinylidene chloride and 1,2-dichloroethylene. Typically, commercial CPVC has in excess of about 60 percent by weight (% by weight) bound chlorine, and is most conveniently prepared by the chlorination of polyvinyl chloride as described in U. S.
Patents Nos. 2,996,489; 3,100,762; 3,334,077; 3,334,078; 3,506,637; and 3,534,013 inter alia. The term CPVC is used herein to define a chlorinated vinyl chloride polymer having in excess of about 60% by weight bound chlorine.
A well-known undesirable characteristic of CPVC resin is that it has inherently low impact properties, a characteristic which is common to vinyl 15 chloride homopolymers. The burgeoning demand for CPVC pipe, vessels, valve bodies and fittings of all kinds, and the fact that an impact-deficient CPVC matrix may be improved by compounding it with impact modifiers, has instigated concerted efforts to develop better impact modified CPVC compositions. Most of these efforts have been channeled towards rigid CPVC applications where 20 acceptable impact strength is critical. Such applications include the manufacture of exterior structural products, rigid panels, pipe and conduitS injection-molded and thermoformed industrial parts, appliance housings, and various types of containers both large and small.
Impact modifiers when used in CPVC reduce the tensile strength and 25 heat dlstortion temperature (HDT) of the resin, and many reduce the pro¢essing heat stability. There are very few modifiers which yield a significant increase in impact strength or improvement in processability of the CPVC resin without vitiating the quallty of the resin. Most elastomeric additives such as conjugated diene homo and copolymers or acrylic polymers which reduce the brittle 30 temperature of vinyl chloride polymers, are ineffective when present in an amount less than about 10% by weight, and if used in a greater amount than 10% adversely a~fect thé high temperature stiffness of the resin. Elastomer additives commonlyused QS conventional impact modifiers are graft copolymers containing butadiene,and ~other copolymers including ~chlorinated polyethylene (CPE), ethylene-vinyl 35 ~ acetate copolymers ~(EVA), acrylate-methacrylate (all ~acrylic) polymers, grafted elastomers based on vinyl chloride (VCG)j nitrile rubbers (BRj, styrene~utadienerubbers, and the like. These conventional impact modifiers are generally used in a substantial amount, that is, an amount sufficient to provide at least a 20% increase ' . ~ ' ' " ' ' . . ' ~ . ' ' ,' ....
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in Izod impaet strength over a non-impact modified CPVC matrix. When any of the foregoing conventional impact moifiers, with the exception of CPE, is used, it is essential that a processing aid be blended into the CPVC composition.
A processing aid is used in melt blending a resin composition to hasten 5 fusion, to smooth out the otherwise rough texture of the composition and to soften the resin so that it is uniformly melt-blended within an acceptably short time.
Easily melt-blended materials such as acrylonitrile-butadiene-styrene resins do not require a processing aid. Commercial polyvinyl chloride (PVC) is conventionally milled with a processing aid, though it can be melt-blended without one; but 10 commerciAlly chlorinated polyvingl chloride (CPVC) has a high melt elelsticity and therefore requires a processing aid or it cannot be acceptably melt-blended. 8y "acceptably melt~lended" I refer to the requirement that CPVC must be melt-blended within a relatively short time, usually no more than 2 or 3 minutes, anddesirably less than 2 mins. Since the fusion temperature of CPVC is relatively 15 high, even long mixing at about 190C can cause evolution of HCl and consequent degradation of the resin. Of course, degradation can be postponed by adding morestabilizer, usually a liquid compound containing tin, or more processing aid, both of which are expensive. However, this is not a practical solution because it increases the cost of the blend and decreases the heat distortion temperature owing to the20 plasticizing effect of the stabilizer or processing aid. Processing at highertemperatures than would be required with the use of a processing aid acceleratesHCl evolution, discolors the resin and results in a low quality end product. Thus, from a prActicfll point of view, a processing aid is essential to melt-blend CPVC.
Since the end use product must have desirable impact strength, from a practical 25 point of view, an impact modifier is also essential in a CPVC composition.
To my knowledge, until this invention, CPE was unlque in that it functioned as a dual function additive or modifier, functioning both as a processing aid and as an impaot modifier, therefore referred to herein as a "pro-modifier".The reasons for this unique and desirable behavior of CPE are not clearly 30 understood. Desirable as this behavior is, it is known that CPE is a more effective processing Aid than impact modifier. Thus, for applications where processability is essential and some impact strength is desirable, CPE alone is used as an impact modifier, but where optimum impact is essential, CPE is generally used in ; combination with one or more of the above-mentioned conventional impact 35 modifiers. Similarly, where processability is a predominant concern, ABS resins, and Cycolac~ L in pflrticular, provide improved processability although from about lO to about 15 parts per hundred parts CPVC resin ~phr) are reguired. PVC, vinylchloride, vinyl chlorlde-vinylidene chloride copolymers and other vinyl or vinylidene ~ Registered U.S.Trademark ; : ' .~ -- . .. .
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~3--chloride based polymers do not produce enough improvement in processability to offset the loss of other physical properties, particularly HDT. Acrylates such as polymethylmethacrylate (PMMA) improve processability but do not contribute an appreciable improvement in impact strength.
Of course, because conventional impact modifiers are rubbery poly-mers, it is eviden~ ~hat relatively large amounts of an impact modifier, greaterthan about 10% by wt of the total resinous components in the composition, will have a beneficial effect upon the processability of CPVC which, by itself, is sodifficult to process. At levels lower than about 10% by wt, conventional impact modifiers exhibit little, if any, improvement in processability, and sometimes even increase the melt elasticity. Some like ethylene-propylene rubber (EPR), show incompatibility with CPVC at levels below 10% by wt.
It is reasonable to expect that a desirable pro-modifier should have certain solubility characteristics compatibly matched to CPVC. Having decided upon the solubility characterisitcs for a pro-modifier, finding the good ones is still a matter of laborious trial and error. With this methodical approach the SD and SDS block copolymers of this invention would have been missed, because they are not expected to have the borderline compatibility characteristics associated with what should be an effective pro-modifier.
All impact modifiers and processing aids, when conventionally used in con~unction with one and another, in whatever combination, are referred to herein as "co-modifiers". It is implicit that a conventional co-modifier, when used alone at a level below about 10 phr, does not provide either sufficiently high impact strength in excess of 2 ft-lb/in Izod impact, or desirable processability, or both, as without an undue sacrifice of HDT and other deslrable physical characteristics of CPVC. For example, yield stress or tensile strength generally drops off llnearlywith increasing concentration of co-modifier which at relatively high levels may be desirable for improving the impact strength. Since, at present, a CPVC
composition with de~irable, relatively high impact strength in excess of 2 ft-lb/in Izod impact, includes an impact modifier and Q processing aid as co-modifiers, matching the co-modifiers for compatibility is a trial and error task which is usually as time-consuming as it is essential. Those skilled in the art, responsible for finding matched co-modifiers, have long sought, without much success, for a dual function or bifunctional modifier which will not vitiate the desirable end-use attributes of CPVC articles. This invention is the successful culmination of thelong search. When used by itself in CPVC, the bifunctional block copolymer is ; ~ referred to herein as a "pro-modifier" because of its dual function as processlng aid and impact modifier. I
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A styrene-butadiene-styrene (SBS) block copolymer has been used as the only impact modifier in vinyl chloride polymers, but it is difficult to blend the SBS block copoly-mer into the vinyl chloride polymer even with a processing aid. For example, S. N. Potepalova et al in Plast. Massy.
8,41 (1973) reported that prolonged mixing was require to get a marginal improvement in impact strength when SBS was used as the sole impact modifier in PVC, It is known, that to toughen plastic synthetic resinous materials with rubber particles dispersed therein, good adhesion must exist be-tween the rubber particles and the plastic (see "Macro-molecular Reviews" by R. P. Kambour, J. Poly. Sci. 7, 1 et seq., 1973). Evidently the requisite adhesion between SBS
and PVC is lacking and there i8 no reason to expect this adhesion to manifest itself in any other vinyl chloride polymer. The reference makes no suggestion that SBS may be used as the sole impact modifier in any other vinyl chloride resin. Since CPVC is sometimes like PVC in its behaviour towards most impact modifiers, it was unexpected that any SBS block copolymer deemed wanting in its effect on the impact properties of PVC would favorably affect the impact properties of CPVC. It is especially surprising that a block (SBS) copolymer, and particularly a dibloc~ (SB) co-polymer, should provide a dual function of processing aid and impact modifier.
Though used as the sole pro-modifier in CPVC
compositions, these block copolymers may also be u~ed as co-modifiers in conjunction with conventional co-modifiers to produce a blended CPVC resin composition which is tailored for specific properties. When so used, that is when the block copolymers are used as co-modifiers with other co-modifiers, the block copolymers produce a synergistic boost in impact effectiveness of the other co-modifier used, with-out any apparent reason for doing so, provided the other co-modifiers are used in a substantial amount sufficient to produce at least a 20% increase in Izod impact strength over the impact strength of matrix without an impact modifier.
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. . , - It has been discovered that a block copolymer of a vinyl aromatic compound and conjugated diene, for example a styrene-diene, or styrene-diene-styrene block copolymer, which classe~ of block copolymer may be designated (SD) and (SDS) respectively, performs a dual function of proces-sing aid and impact modifier (hereafter referred to as a "pro-modifier") in chlorinated polyvinyl chloride (CPVC).
It has further been discovered that improvement in the impact properties of CPVC due to presence of the b~ock copolymer pro-modifier isunexpectedly better than with con-ventional impact modifiers and processing aids, when compared on a weight basis. Modifiers and processing aids, when used either independently or in combination with one and another are referred to herein as "co-modifiers".
It has been been discovered that a ~D or SDS block copolymer, or mixtures thereof, may be used in conjunction with one more conventional impact modifiers and~or processing aids, that is, as a co-modifier to tailor the impact and processing characteristics of CPVC for any predetermined application.
It is therefore a general object of this inven-tion to provide a novel CPVC impact resistant composition comprising (a) a chlorinated vinyl chloride polymer, and (b) a pro-modifier block copolymer, for example, an SD or SDS block copolymer, optionally including additives for desirable color, stability and the like. This novel compo-sition provides a surprisingly advantageous combination of processability, heat stability, HDT retention and impact strength.
~ In accordance with the invention there i9 provided a normally rigid thermoplastic composition comprising (a) a matrix comprising a chlorinated vinyl chloride resin, and (b) a dual function processing aid and impact modifier, or pro-modifier, consisting essentially of a block copolymer of a vinyl aromatic compound (S) and a conjugated diene (D), wherein said vinyl aromatic compound (S) is selected from the gxoup consisting of styrene, ~-methyl styrene, vinyl toluene, vinyl xylene, and naphthalene, said conjugated diene (D) is selected from the group consisting of buta-diene, isoprene, 1,3-pentadiene,and 2,3-dimethyl butadiene, : :A
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5 ~ L177 - a-and said pro-modifier is present in an amount in the range from about 1 percent to about 10 percent by weight based on the total resinous components of said composition.
In another aspect of the invention there is pro-vided a method of preparing a normally rigid thermoplastic article comprising melt blending the composition of the invention to obtain a uniform melt, and shaping the melt to form the article.
It is a specific object of this invention to provide a rigid CPVC plastic formulation of exceptional impact resistance, which formulation is an easily melt-blended composition comprising (a) CPVC polymer having primary particles in the size range from about 2500 A
0.25~ ) to about 2~ (micron), and (b) an SD or SDS block copolymer pro-modifier having primary particles in the size range from about 200 A to about 1 micron.
It is another specific object of the invention to provide a rigid CPVC plastic formulation with surprising impact strength and processability coupled with low shrink-age, in which a linear block copolymer of the styrene-butadiene-styrene (SBS) type or the styrene-butadiene (SB) type, or a radial block copolymer of the SBS type with vinyl aromatic terminal blocks, may be used as a first co-modifier with at least one other second co-modifier which is independently selected from a conventional impact modifier and a processing aid for CPVC.
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Brief Description of the Drawings The foregoing and other obje~ts and advantages of my invention will appear more fully from the following description of preferred embodiments of theinvention, some of which description is set forth in conjunction with the accompanying drawing wherein:
~igure 1 graphically illustrates the effect on impact strength of SBS
pro-modifier in parts per 100 parts of total resin (phr) when the SBS is melt-blended into a CPVC matrix.
Figure 2 graphically illustrates the effect on impact strength of SBS
pro-modifier according to its contribution of rubber in the composition, and shows the synergistic effect of that contribution.
All references to t'the block copolymer" in this specification refer to an SD or SDS block copolymer as described in more detail in the following detailed description of preferred embodiments of the invention.
Detailed Description of Preferred Embodiments In a preferred embodiment of this invention, chlorinated polyvinyl chloride (CPVC) containing at least 60% by weight bound chlorine, forms the matris, continuous phase, continuum or major phase in which is usually blended plasticizers, antioxidants, pigments, ultraviolet light stabilizers, processing aids, impact modifiers and the like. The following description and observations and tests on illustrative examples of various CPVC recipes compounded with SD or SDS blockcopolymer pro-modifier as the sole modifier, or with plural co-modifiers including the block aopolymer, disregards the use of all ingredients except those related to impact performance. It is expected that those skilled in the art can effectively; ~ 25 utilize tho~e ingredi~snts which have no special lmpact-lmproving characterlsti¢s in ¢on~unction with the teachings of this invent~on.
The impact strength of chlorinated vinyl chloride polymers generally, and CPVC in particular, in the range from about 0.5 to about 2.0 ft-lb/in is known to be approximately directly correlatable to the concentration (wt %) of rubber in the cPVa. By "rubber" I refer to the rubbery content of an elastomer impact modlfier, such as, for example, the rubber content of an overpolymerized graft copolymer in which a hard resin i~ grafted on a rubbery center (hence referred to herein as "hard shell" resin). In gener~l, in this range of about 0.5 to about 2.0 ft-lblin impact strength, the higher ~fhe wt% rubber, the higher the impact strength.
: 35: Typically, where more than one conventional impact modifier iB used, the impact strength obtained is~approximately directly correlatable to the cumulative wt %
rubber ¢ontent.
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: .. . , _ 1~ 77 It is not the primary purpose of this invention to provide a rigid CPVC
composition having the highest possible impact strength, but to provide desirable impact strength and ease of processing by using less conventional impact modifier and processing aid than normally used to provide preselected impact and 5 processability values. ~his is made possible by replacing some, and more preferably all, of the conventional impact modifiers and processing aids with the SD or SDSblock copolymer. In many instances, the use of pro-modifier alone, in an amount less than the combined weight of conven~ional impact modifier and processing aid, provides the same impact strength and processability.
In general, the more co-impact modifier used, the greater the impact strength, and the cost-effectiveness of a co-modifier is evaluated by comparing impact strength versus parts of c~modifier per hundred parts of vinyl chloride resin matrix.
Any comparison of co-modifiers must take into account the fact that their rubber contents vary widely. Since improved impact strength is attributable to the weight percent (wt %) rubber, and the rubber contents vary, formulations are compared at constant wt % rubber, or constant parts rubber per hundred parts resin (phr), and the total weight of resin includes CPVC, polystyrene from the SBS
(say) ultra-modifier block copolymer used, and resin from grafted impact modifier.
In a first embodiment, the invention is concerned with the use of the SD or SDS linear or radial block copolymer as the only modifier, that is as a "pro-modifier", in commercially produced CPVC.
In a second embodiment, this invention is concerned with the use of the SD or SDS, linear or radial block copolymer conjointly with at least one other modifier, whqther an impact modifier or processing aid, or both, in commerciallyproduced CPVC. When plural modif{ers are used, one of which 1s the block copolymer, each of the rnodifiers includlng the block copolymer i9 referred to as a "co-modifier", and the effect on impact strength and processability of the combined co~modifiers may be, and generally is, unexpectedly more beneficial than their individual and separate, essentially merely additive effects. In this second embodiment of this invention, where a conventional impact modifier (a first co-modifer), is used with an SD or sbs block copolymer (as a second co-modifer), anincrease in impact strength is obtained which is unexpectedly greater than that obtained if the combined wt % rubber was present in the first co-modifier alone.Quite commonly a boost in impact strength is obtained with the two combined co-modifiers, despite the total wt % rubber therein being less than that necessary in a conventional impact modifier which produces comparable impact resistance. Total wt % rubber is the sum of the rubbery contents o~ the modifiers used, whether it be ,~ ,i ' ~' .
' ' the diene content of the block copolymer, or the diene or other similQr rubber content of a conventional c~modifier, in parts by weight per 100 parts by weightof CPVC composition.
There is provided in the first embodiment of this invention, an impact-modified thermoplastic composition free of conventional impact modifiers and processing aids, cs)mprising (a) a matrix comprising a chlorinated polyvinyl chloride polymer, and (b) a block copolymer pro-modifier consisting essentially of Q vinyl aromatic compound (S) and a conjugated diene (D) of the linear block, or radial block type, blocks ~D) being of either lower or higher average molecular weight than those of blocks (S), component (b) being present in an amount in the range from about 1 to about 10 wt %, and preferably from about 2 to about 8 wt % of the total resinous components of the composition. Component (b) is typically melt-Mended into the matrix and the CPVC blend so produced exhibits the same properties as conventionally modified CPVC blends, except that it has better processability and impact properties. The inherently excellent properties of CPVC, namely, low smoke, and low flammability, may now be obtained along with excellent impact strength and processability at lower cost than prior art CPVC
blends.
In general, the processability of polymers of halogenated vinyl monomers, and particularly PVC and CPVC, is so poor that processing aids must bemelt-blended into the matrix along with the impact modifier. Typically a processing aid is a random copolymer of styrene and acrylonitrile, or a copolymer of ~-methyl styrene and methyl methacrylate, or polymethylmethacrylate, any one or more o~ which is used in an amount less than about 10 % by wt, and preferably in an amount in the range from about 1% to about 5% by wt.
The preclse mechanism by which the presence of a small amount of pro-modifier, less than 10% by wt, contrlbutes to the Impact strength and processability of the CPVC, is unknown, but a mechanism is hypothesized. During molten polymer blending of the pro-modifier into the CPVC matrix, a broad distributIon of rubber particle sizes occurs. The pro-modifier contributes very small partlcles in the size range~from about 200 R to about 1000 Q (Angstrom ; ~ units), as well as some larger particles in the range from 1000 A to about 10,000 A.
` In particular, durlng melt blending, there is agglomeration of some rubber particles which further contributes to a broad particle size distribution in the composition.
35~ Further, the glass transition temperature Tg of the polybutadiene block in the block copolymer is subst&ntially lower than the Tg of conventional impact modifiers, and thus improves impact strength. Yet another factor contributing to :
.
' ~ ' the desirable imp~ct and processing qualities of the pro~modified CPVC may be the inclusion of polystyrene blocks in the dispersed polybutadiene rubber particles to increase the volume of rubbery particles.
The chlorinated polyvinyl chloride polymers (CPVC) used in this invention may be chlorinated homopolymers of vinyl chloride, or copolymers of chlorinated vinyl chloride and other monomers copolymeri~able therewith, and CPVC constitutes in excess of 50% by weight of the composition of this invention.
More preferably, the matrix of CPVC is present in the range from sbout 70% to about 95% by weight of the composition, the remainder being block copolymer pro-modifier. Other additives, not`uniformly distributed within the CPVC matrix, andnot used primarily for impact modification or processability, are disregarded for the purpose of this invention. Examples of other monomers referred to include vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, and the like; alpha-olefins, such as ethylene, propylene, butylene and the like; and alkyl acrylates or methacrylates having up to 18 carbon atoms in the alkyl moiety.
Preferred chlorinated polymers include polyvinyl chloride, and to the extent that they can be chlorinated, chlorinated vinyl chloride/vinyl acetate copolymers, and chlorinated vinyl chloride/ethylene copolymers, the former containing from about 5 to about 20% by weight of vinyl acetate, and the latter containing from about 0.3 to about 1.9% by weight ethylene copolymerized therein. Most preferred are general purpose types of commercially available CPVC produced as particularly described in U. S. patent No. 2,946,489.
Block copolymers of vinyl aromatic compounds and conjugated dienes are described in KeMedy et al., (Editor) 'tPolymer Chemistry of Synthetic Elastomer9", Interscience, Vol. 23, Part II, 1969, pages 533-559~ R. Zelinski and C.
W. Ch11ders "Rubber Chemistry and Technology" Vol. 41, page lB1 et seg. (1968);
;~ and "Technology" Vol. 43, page 22 et seq. (1970). The block copolymers are of the SD or SDS type in which the relative ratios of the homopolymer blocks can vary. In the compositions of this invention, the block copolymer's blocks D will always be those of R con~ugated diene, e.g., butadiene; isoprene; 1,3-pentadiene; 2,3-dimethyl-butadiene, and the like or mixtures of the foregoing; and blocks S willalways be derived from a vinyl aromatic compound, e.g., styrene, c~ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, or mixtures of any of the foregoing. In the~ most preferred compositions, the block copolymer pro-modifierwill ~have blocks S comprised of polystyrene, and blocks B comprised of polybutadiene.
The pro-modifier necessarily has either a linear block or a radial ~; teIeblock structure, "teleblock" being used to designate copolymers with terminal - , ' ,. ' '':
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block segments of one of the monomers used to produce them. Preferred are linearblocks having polyvinyl aromatic terminal blocks, and radial trichain and tetra-chain Mocks having polyvinyl aromatic terminal blocks. Of course, linear diblocks have terminal S and D blocks, and in all the SDS copolymers the terminal blocks will be vinyl aromatic, e.g., from styrene. ~'Radial" means a network in which the polystyrene blocks make the rubber thermoplastic tby virtue of the weight content) and association provides a network of plastic areas connected by flexible diene rubber blocks so the material has excellent mechanical properties without vulcanization. Although they are rubbery solids, the linear block and radial teleblock polymers soften and flow with heat and can be molded and extruded in the same manner as other thermoplastic materi~s. They can be remolded repeatedly without loss in properties. The precise structure of the block copolymer, that is, whether it is a diblock, triblock, or mixed polyblock copolymer is not critical, nor is its molecular weight, provided it is in the range specified hereinafter.
The ratio of the co-monomers can vary broadly, and the average molecular weight (mol wt) of combined blocks (D) may be either less than or greater than that of combined terminal blocks (S). It is preferred that the mol wt of combined blocks (D) be greater than the mol wt of combined blocks (S), to introduce desirable rubber into the composition. Higher rubber content is preferred if optimum impact strength is to be contributed by the pro-modifier. Thus, styrene-butadiene (SB) block copolymers are particularly useful and desirable since melt-blending and processing the components is relatively easy. Typically the average mol wt of the block copolymer is in the range from about 50,000 to about 25 300,000, and the average wt % of the combined vinyl aromatic terminal blocks (S) will range from about 20% to about 50%. In preferred block copolymers the aromatic compound units comprise a minor fraction by weight of the block copolymer,and the diene units the major fraction from about 60% to about 80%.
The block copolymers are made by an organolithium initiated polyme~
30 ization process in hydrocarbon solution using, for example, butadiene and styrene or other diene and vinyl aromatic monomers as is described in Kennedy et al, mentioned above.
, ; In one process, a SDS block copolymer is prepared by dissolving the conjugated diene, e.g., butadiene, in an aromatic hydrocarbon solvent, e.g., xylene, toluene, etc., and adding 0.3 to 7.5 millimoles/100 parts of monomer, of an organolithium initiator, e.g., n-butyl lithium, etc. Polymerization of the diene is aompleted and then the vinyl aromatic compound is added and polymerization of this is completed to form the block copolymer. The product is precipitated and deactivated, e.g., with alcohol, such as ethanol or isopropanol and purified by , ' ~. ' , ' ~
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-redissolving in hydrocarbon and reprecipitating with alcohol.
In another process, the block copolymer is formed using, e.g., a secondary or tertiary alkyl lithium compound at about 100-2,000 parts per million based on the total weight of the monomers and a polymerization temperature in the range from about 20C to about 65C. For example, sty-rene is dissolved in cyclohexane at 32C, and treated with 5,530 parts per million of secondary butyl lithium. After polymerization is complete, isoprene is injected and poly-merization is continued at 55C-57C. The product can be recovered as described above.
Monovinyl-substituted aromatic hydrocarbons and conjugated diene block copolymers are commercially avialable from Shell Chemical Company under the trademark KRATON.
These SDS block copolymers may be prepared by anionic solu-tion polymerization methods with organo-metallic catalysts as more fully described in U.S. Patent No. 3,265,765, and the Encyclopedia of Polymer Science and Technology, 15, pgs 508-530, Interscience Publishers, NYC (1971). The commonly used designations of SBS for styrene-butadiene-styrene and SIS for styrene-isoprene-styrene block copolymers, are used for bre~ity, in this specification.
Other commercially available SBS blockcopolymers are useful promodifers; for example, the block copolymer resins available as Solprene* rubbers, arld K-resins* KRO-l and KRO-3 from Phillips Petroleum Company, which resins are more fully di~closed in U.S. Patent No. 3,639,517 inter alia.
KRO-l contains about 73.6 wt percent of pure polystyrene blocks, balance polybutadiene blocks, the polybutadiene hav-ing a substantial percent of the cis-1,4-microstructure. The intrinsic viscosity in a typical ~ample is 0.67 dl/g (in chloroform at 25C). KRO-3 is a radial teleblock copolymer, like KRO-l, but the styrene content is about 75.8 wt percent and the intrinsic viscosity is slightly lower, about 0.64 dl/g. The glass transition point of the polybutadiene seg-ments in each case is about -90C. KRO-l shows a bimodal molecular weight distribution by gel phase chromatography.
KRO-3 has a smaller, low molecular weight peak.
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1~11177 ., -lla-The method of forming the polymer composition is not critical, prior art blending techniques being suitable.
The preferred method comprises melt blending the resinous components and additives in any of several ways, including providing the components in powder, granular, filamentous, or other convenient form, extruding the blend and chopping into pellets for molding to preselected shape by molding means conventionally used to mold normally solid thermo-plastic compositions. In some instances the components of the composition may be utilized as a blend of powders which blend may be directly formed into rigid shapes.
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for example, by extrusion.
The importance of the boost in impact properties contributed by a relatively small smount of SDS pro-modifier generally less than 10 wt % of the resinous components of the composition, is more particularly appreciated because5 the boost is achieved in conjunction with surprisingly good processability. Though, as with conventional impact modifiers and processing aids, particularly a processing aid such as CPE, there is some loss of room temperature tensile properties and HDT, but this loss is more acceptable.
In the second embodiment of this invention referred to hereinabove, 10 the CPVC matrix is conjointly modified by melt-blending with an SD or SDS block copolymer, and a conventional graft copolymer of the hard shell resin type.
Preferably, a processing aid is a~so melt-blended into the matrix. Since the block copolymer is now used in conjunction with conventional modifiers, it is now referred to as a co-modifier, as are the conventional impact modifier and 15 processing aid. In this embodiment, the composition comprises (a) a matrix comprising a chlorinated polyvinyl chloride polymer, (b) an SD or SD~ block copolymer co-modifier described hereinabove, and (c) a conventional impact modifier, component (b) being present in an amount in the range from about 1 to about 10 wt ~6, and preferably from about 2 to about 8 wt % of the total resinous 20 components of the composition, and component (c) being present in an amount in the range from about 1 to about 10 wt %, and preferably from about 2 to about 5 wt % of the total resinous components of the composition.
The contribution of the conventional impact modifier with respect to improving the impact strength is not critical. In general, when an SD or SDS blo~k 25 copolymer is used as a co-modifier with a conventional impact modifier such as a graft copolymer, and optionally, with a processing aid, the graft copolymer is present in the matrix in an amount sufficient to contribute substantial impact strength to the rigid CPVC. By "substantial" impact strength I refer to an increase in Izod impact strength of at least 20% oYer the impact strength of CPVC without30 an impact modifier.
In a CPVC composition including the block copolymer and another co-modifier, a synergistic effect is obtained as evidenced by an unexpected boost in impact strength of the melt-blended composition. Though the mechanism by which such a boost in impact strength is obtained is not clearly understood, it is 35 hypothesized that the block copolymer produces, during melt-blending, a broaddistribution of rubber particle sizes. This hypothesis is consistent with that ; proffered to explain the boost in impact strength of the block copolymer used as a pro-modifier. It is appreciated that distribution of rubber particle sizes over a wide range, by itself, does not offer a satisfactory explanation for the excellent , .. ... . . .. . ..
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- . . . -: - ~ . . . . -processability of CPVC modified with the block copolymer, and it may be that unidentified physico-chemical effects peculiar to the block copolymer play an essential role. The fact remains that the block copolymer produces impact strength and processability which is demonstrably far greater than one might 5expect for so small (low wt %) a contribution of rubber. For example by replacing from 20% to about 40% by wt of the rubber from a graft copolymer co-modifier, with rubber (butadiene) from an SB or SBS co-modifier, an unexpected boost in impact strength is obtained. It appears that the separate particles of block copolymer and graft copolymer, in conjunction with their chemical affinity to form 10large agglomerates, in addition to a wide size range of others, eccounts for the special effects attributable to the block copolymer.
Suitable graft copolymers are those conventionally used as impact modifiers for vinyl chloride polymers, and for the most part, commercially available graft copolymers are preferred. These graft copolymers chracteristically 15have a rubbery center upon which is graft copolymerized a shell of hard resin. The process for polymerization of the rubbery center and subsequent overpolymeriza-tion of the hard resin by graft copolymerization, is well known. Typical preferred graft copolymerized impact modifiers used for vinyl chloride polymers are those of the MBS type, commercially available as B~,A-III S and BTA III N from Kureha Co.;
20those of the ABS type, available as Blendex 301 and 311 from Marbon; and those of the PMMA/PBA type, available as KM323B from Rohm ~ Haas.
In each of the embodiments of the composition of this invention, at impact strain rates, the beneficial effect of the SDS or SD block copolymer is manifested in R lower yield stress (craze initiation) and in an increased elongation 25to break (plasticity). The net effect, assuming the optiumum amount i8 not exceeded, is that of adding more rubber as co-modifier without actually having done 90.
The boost in impact strength attributable to the SDS block copolymer is not Q transient effect such as sometimes results from frozen-in effects during 30rapid cooling. The impact strength and other desirable properties of the composition of this invention persist even after the composition is annealed below its Tg. The composition of this invention may be formulated in the same physicalmanncr, utilizing the same equipment, as known conventionally impact-modified chlorinated polyvinyl chloride polymers, but with appropriate changes in the recipes 35to compensate for the~ fact that the SDS or SD block copolymers generally soften ! `~ ~ and hasten fusion of the CPVC ingredients-It is of great commercial importance that hastening of fusion of CPVC
while melt-blending the block copolymer into the CPVC decreases the time .
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1~11177 required, yet the novel CPVC blend exhibits greater impact strength over a broader temperature range than do conventional CPVC blends.
The invention will be more fully understood and appreciated by the further description of the specific embodiments set forth in the examples which 5 follow. All parts and percentages refer to weight unless otherwise stated.
The îollowing recipes with ingredients as specified, are mechanically blended in a 4" Getty mill for about 4 minutes at about 200C, and compression-molded at about 215C in a l~boratory press.
In examples 1 - 5 set forth herein in Table I hereinbelow, GEON*603-10 x560 CPVC, available from The B.F.Goodrich Company, is master-batched with varying amounts of KRATON 1102 pro-modifier, which is a thermoplastic linear SBS block copolymer available from Shell Chemical Co. GEON 603x560 CPVC
contains from about 65.3% to about 65.9% bound chlorine, and has an inherent viscosity in the range from about 0.90 to about 0.95 in cyclohexanone. Each b~.tch of 100 parts of CPVC contains 1.125 parts lubricant, such as MICROTHENE 510 polyethelene; 2.0 parts stabilizer, such as T-31 THERMOLITl~tabilizer, which is a dibutyl tin bisisooctylthioglycollate. Each batch is milled at 200C for 4 minutes and compression molded into test pieces. The polyethylene lubricant provides lubricity and prevents sticking of the resin to the rolls. A lubricant does not function as a processing aid in that the lubricant does not aid fusion and does not substantially smoothen out or soften the stock. Pigments, such as TiO2 powder inthe form of rutile, if added, impart opacity to the blend and serve as a base for coloration. The Izod impact strength value tabulated for each example is the average of six test pieces. S8mples with no pro-modifier, that is, with zero rubber content, had an impact strength of 0.50 + 0.1 ft-lb/ln.
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Ex.CPVC matrixPro-modifier Rubber Izod Std.
No.Geon 603x560Kraton 1102 content~* impact dev.
g g phr ft-lb/in ( +S ) 100 2.0 0.0 1.1 0.09
Background of the Invention It is well known that a chlorinated vinyl polymer referred to as chlorinated polyvinyl chloride (CPVC) has excellent high temperature performance5 characteristics, among other desirable physical properties. CPVC resin is commercially available as a mixed polymeric structure of vinyl chloride, vinylidene chloride and 1,2-dichloroethylene. Typically, commercial CPVC has in excess of about 60 percent by weight (% by weight) bound chlorine, and is most conveniently prepared by the chlorination of polyvinyl chloride as described in U. S.
Patents Nos. 2,996,489; 3,100,762; 3,334,077; 3,334,078; 3,506,637; and 3,534,013 inter alia. The term CPVC is used herein to define a chlorinated vinyl chloride polymer having in excess of about 60% by weight bound chlorine.
A well-known undesirable characteristic of CPVC resin is that it has inherently low impact properties, a characteristic which is common to vinyl 15 chloride homopolymers. The burgeoning demand for CPVC pipe, vessels, valve bodies and fittings of all kinds, and the fact that an impact-deficient CPVC matrix may be improved by compounding it with impact modifiers, has instigated concerted efforts to develop better impact modified CPVC compositions. Most of these efforts have been channeled towards rigid CPVC applications where 20 acceptable impact strength is critical. Such applications include the manufacture of exterior structural products, rigid panels, pipe and conduitS injection-molded and thermoformed industrial parts, appliance housings, and various types of containers both large and small.
Impact modifiers when used in CPVC reduce the tensile strength and 25 heat dlstortion temperature (HDT) of the resin, and many reduce the pro¢essing heat stability. There are very few modifiers which yield a significant increase in impact strength or improvement in processability of the CPVC resin without vitiating the quallty of the resin. Most elastomeric additives such as conjugated diene homo and copolymers or acrylic polymers which reduce the brittle 30 temperature of vinyl chloride polymers, are ineffective when present in an amount less than about 10% by weight, and if used in a greater amount than 10% adversely a~fect thé high temperature stiffness of the resin. Elastomer additives commonlyused QS conventional impact modifiers are graft copolymers containing butadiene,and ~other copolymers including ~chlorinated polyethylene (CPE), ethylene-vinyl 35 ~ acetate copolymers ~(EVA), acrylate-methacrylate (all ~acrylic) polymers, grafted elastomers based on vinyl chloride (VCG)j nitrile rubbers (BRj, styrene~utadienerubbers, and the like. These conventional impact modifiers are generally used in a substantial amount, that is, an amount sufficient to provide at least a 20% increase ' . ~ ' ' " ' ' . . ' ~ . ' ' ,' ....
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in Izod impaet strength over a non-impact modified CPVC matrix. When any of the foregoing conventional impact moifiers, with the exception of CPE, is used, it is essential that a processing aid be blended into the CPVC composition.
A processing aid is used in melt blending a resin composition to hasten 5 fusion, to smooth out the otherwise rough texture of the composition and to soften the resin so that it is uniformly melt-blended within an acceptably short time.
Easily melt-blended materials such as acrylonitrile-butadiene-styrene resins do not require a processing aid. Commercial polyvinyl chloride (PVC) is conventionally milled with a processing aid, though it can be melt-blended without one; but 10 commerciAlly chlorinated polyvingl chloride (CPVC) has a high melt elelsticity and therefore requires a processing aid or it cannot be acceptably melt-blended. 8y "acceptably melt~lended" I refer to the requirement that CPVC must be melt-blended within a relatively short time, usually no more than 2 or 3 minutes, anddesirably less than 2 mins. Since the fusion temperature of CPVC is relatively 15 high, even long mixing at about 190C can cause evolution of HCl and consequent degradation of the resin. Of course, degradation can be postponed by adding morestabilizer, usually a liquid compound containing tin, or more processing aid, both of which are expensive. However, this is not a practical solution because it increases the cost of the blend and decreases the heat distortion temperature owing to the20 plasticizing effect of the stabilizer or processing aid. Processing at highertemperatures than would be required with the use of a processing aid acceleratesHCl evolution, discolors the resin and results in a low quality end product. Thus, from a prActicfll point of view, a processing aid is essential to melt-blend CPVC.
Since the end use product must have desirable impact strength, from a practical 25 point of view, an impact modifier is also essential in a CPVC composition.
To my knowledge, until this invention, CPE was unlque in that it functioned as a dual function additive or modifier, functioning both as a processing aid and as an impaot modifier, therefore referred to herein as a "pro-modifier".The reasons for this unique and desirable behavior of CPE are not clearly 30 understood. Desirable as this behavior is, it is known that CPE is a more effective processing Aid than impact modifier. Thus, for applications where processability is essential and some impact strength is desirable, CPE alone is used as an impact modifier, but where optimum impact is essential, CPE is generally used in ; combination with one or more of the above-mentioned conventional impact 35 modifiers. Similarly, where processability is a predominant concern, ABS resins, and Cycolac~ L in pflrticular, provide improved processability although from about lO to about 15 parts per hundred parts CPVC resin ~phr) are reguired. PVC, vinylchloride, vinyl chlorlde-vinylidene chloride copolymers and other vinyl or vinylidene ~ Registered U.S.Trademark ; : ' .~ -- . .. .
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~3--chloride based polymers do not produce enough improvement in processability to offset the loss of other physical properties, particularly HDT. Acrylates such as polymethylmethacrylate (PMMA) improve processability but do not contribute an appreciable improvement in impact strength.
Of course, because conventional impact modifiers are rubbery poly-mers, it is eviden~ ~hat relatively large amounts of an impact modifier, greaterthan about 10% by wt of the total resinous components in the composition, will have a beneficial effect upon the processability of CPVC which, by itself, is sodifficult to process. At levels lower than about 10% by wt, conventional impact modifiers exhibit little, if any, improvement in processability, and sometimes even increase the melt elasticity. Some like ethylene-propylene rubber (EPR), show incompatibility with CPVC at levels below 10% by wt.
It is reasonable to expect that a desirable pro-modifier should have certain solubility characteristics compatibly matched to CPVC. Having decided upon the solubility characterisitcs for a pro-modifier, finding the good ones is still a matter of laborious trial and error. With this methodical approach the SD and SDS block copolymers of this invention would have been missed, because they are not expected to have the borderline compatibility characteristics associated with what should be an effective pro-modifier.
All impact modifiers and processing aids, when conventionally used in con~unction with one and another, in whatever combination, are referred to herein as "co-modifiers". It is implicit that a conventional co-modifier, when used alone at a level below about 10 phr, does not provide either sufficiently high impact strength in excess of 2 ft-lb/in Izod impact, or desirable processability, or both, as without an undue sacrifice of HDT and other deslrable physical characteristics of CPVC. For example, yield stress or tensile strength generally drops off llnearlywith increasing concentration of co-modifier which at relatively high levels may be desirable for improving the impact strength. Since, at present, a CPVC
composition with de~irable, relatively high impact strength in excess of 2 ft-lb/in Izod impact, includes an impact modifier and Q processing aid as co-modifiers, matching the co-modifiers for compatibility is a trial and error task which is usually as time-consuming as it is essential. Those skilled in the art, responsible for finding matched co-modifiers, have long sought, without much success, for a dual function or bifunctional modifier which will not vitiate the desirable end-use attributes of CPVC articles. This invention is the successful culmination of thelong search. When used by itself in CPVC, the bifunctional block copolymer is ; ~ referred to herein as a "pro-modifier" because of its dual function as processlng aid and impact modifier. I
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A styrene-butadiene-styrene (SBS) block copolymer has been used as the only impact modifier in vinyl chloride polymers, but it is difficult to blend the SBS block copoly-mer into the vinyl chloride polymer even with a processing aid. For example, S. N. Potepalova et al in Plast. Massy.
8,41 (1973) reported that prolonged mixing was require to get a marginal improvement in impact strength when SBS was used as the sole impact modifier in PVC, It is known, that to toughen plastic synthetic resinous materials with rubber particles dispersed therein, good adhesion must exist be-tween the rubber particles and the plastic (see "Macro-molecular Reviews" by R. P. Kambour, J. Poly. Sci. 7, 1 et seq., 1973). Evidently the requisite adhesion between SBS
and PVC is lacking and there i8 no reason to expect this adhesion to manifest itself in any other vinyl chloride polymer. The reference makes no suggestion that SBS may be used as the sole impact modifier in any other vinyl chloride resin. Since CPVC is sometimes like PVC in its behaviour towards most impact modifiers, it was unexpected that any SBS block copolymer deemed wanting in its effect on the impact properties of PVC would favorably affect the impact properties of CPVC. It is especially surprising that a block (SBS) copolymer, and particularly a dibloc~ (SB) co-polymer, should provide a dual function of processing aid and impact modifier.
Though used as the sole pro-modifier in CPVC
compositions, these block copolymers may also be u~ed as co-modifiers in conjunction with conventional co-modifiers to produce a blended CPVC resin composition which is tailored for specific properties. When so used, that is when the block copolymers are used as co-modifiers with other co-modifiers, the block copolymers produce a synergistic boost in impact effectiveness of the other co-modifier used, with-out any apparent reason for doing so, provided the other co-modifiers are used in a substantial amount sufficient to produce at least a 20% increase in Izod impact strength over the impact strength of matrix without an impact modifier.
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. . , - It has been discovered that a block copolymer of a vinyl aromatic compound and conjugated diene, for example a styrene-diene, or styrene-diene-styrene block copolymer, which classe~ of block copolymer may be designated (SD) and (SDS) respectively, performs a dual function of proces-sing aid and impact modifier (hereafter referred to as a "pro-modifier") in chlorinated polyvinyl chloride (CPVC).
It has further been discovered that improvement in the impact properties of CPVC due to presence of the b~ock copolymer pro-modifier isunexpectedly better than with con-ventional impact modifiers and processing aids, when compared on a weight basis. Modifiers and processing aids, when used either independently or in combination with one and another are referred to herein as "co-modifiers".
It has been been discovered that a ~D or SDS block copolymer, or mixtures thereof, may be used in conjunction with one more conventional impact modifiers and~or processing aids, that is, as a co-modifier to tailor the impact and processing characteristics of CPVC for any predetermined application.
It is therefore a general object of this inven-tion to provide a novel CPVC impact resistant composition comprising (a) a chlorinated vinyl chloride polymer, and (b) a pro-modifier block copolymer, for example, an SD or SDS block copolymer, optionally including additives for desirable color, stability and the like. This novel compo-sition provides a surprisingly advantageous combination of processability, heat stability, HDT retention and impact strength.
~ In accordance with the invention there i9 provided a normally rigid thermoplastic composition comprising (a) a matrix comprising a chlorinated vinyl chloride resin, and (b) a dual function processing aid and impact modifier, or pro-modifier, consisting essentially of a block copolymer of a vinyl aromatic compound (S) and a conjugated diene (D), wherein said vinyl aromatic compound (S) is selected from the gxoup consisting of styrene, ~-methyl styrene, vinyl toluene, vinyl xylene, and naphthalene, said conjugated diene (D) is selected from the group consisting of buta-diene, isoprene, 1,3-pentadiene,and 2,3-dimethyl butadiene, : :A
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5 ~ L177 - a-and said pro-modifier is present in an amount in the range from about 1 percent to about 10 percent by weight based on the total resinous components of said composition.
In another aspect of the invention there is pro-vided a method of preparing a normally rigid thermoplastic article comprising melt blending the composition of the invention to obtain a uniform melt, and shaping the melt to form the article.
It is a specific object of this invention to provide a rigid CPVC plastic formulation of exceptional impact resistance, which formulation is an easily melt-blended composition comprising (a) CPVC polymer having primary particles in the size range from about 2500 A
0.25~ ) to about 2~ (micron), and (b) an SD or SDS block copolymer pro-modifier having primary particles in the size range from about 200 A to about 1 micron.
It is another specific object of the invention to provide a rigid CPVC plastic formulation with surprising impact strength and processability coupled with low shrink-age, in which a linear block copolymer of the styrene-butadiene-styrene (SBS) type or the styrene-butadiene (SB) type, or a radial block copolymer of the SBS type with vinyl aromatic terminal blocks, may be used as a first co-modifier with at least one other second co-modifier which is independently selected from a conventional impact modifier and a processing aid for CPVC.
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Brief Description of the Drawings The foregoing and other obje~ts and advantages of my invention will appear more fully from the following description of preferred embodiments of theinvention, some of which description is set forth in conjunction with the accompanying drawing wherein:
~igure 1 graphically illustrates the effect on impact strength of SBS
pro-modifier in parts per 100 parts of total resin (phr) when the SBS is melt-blended into a CPVC matrix.
Figure 2 graphically illustrates the effect on impact strength of SBS
pro-modifier according to its contribution of rubber in the composition, and shows the synergistic effect of that contribution.
All references to t'the block copolymer" in this specification refer to an SD or SDS block copolymer as described in more detail in the following detailed description of preferred embodiments of the invention.
Detailed Description of Preferred Embodiments In a preferred embodiment of this invention, chlorinated polyvinyl chloride (CPVC) containing at least 60% by weight bound chlorine, forms the matris, continuous phase, continuum or major phase in which is usually blended plasticizers, antioxidants, pigments, ultraviolet light stabilizers, processing aids, impact modifiers and the like. The following description and observations and tests on illustrative examples of various CPVC recipes compounded with SD or SDS blockcopolymer pro-modifier as the sole modifier, or with plural co-modifiers including the block aopolymer, disregards the use of all ingredients except those related to impact performance. It is expected that those skilled in the art can effectively; ~ 25 utilize tho~e ingredi~snts which have no special lmpact-lmproving characterlsti¢s in ¢on~unction with the teachings of this invent~on.
The impact strength of chlorinated vinyl chloride polymers generally, and CPVC in particular, in the range from about 0.5 to about 2.0 ft-lb/in is known to be approximately directly correlatable to the concentration (wt %) of rubber in the cPVa. By "rubber" I refer to the rubbery content of an elastomer impact modlfier, such as, for example, the rubber content of an overpolymerized graft copolymer in which a hard resin i~ grafted on a rubbery center (hence referred to herein as "hard shell" resin). In gener~l, in this range of about 0.5 to about 2.0 ft-lblin impact strength, the higher ~fhe wt% rubber, the higher the impact strength.
: 35: Typically, where more than one conventional impact modifier iB used, the impact strength obtained is~approximately directly correlatable to the cumulative wt %
rubber ¢ontent.
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: .. . , _ 1~ 77 It is not the primary purpose of this invention to provide a rigid CPVC
composition having the highest possible impact strength, but to provide desirable impact strength and ease of processing by using less conventional impact modifier and processing aid than normally used to provide preselected impact and 5 processability values. ~his is made possible by replacing some, and more preferably all, of the conventional impact modifiers and processing aids with the SD or SDSblock copolymer. In many instances, the use of pro-modifier alone, in an amount less than the combined weight of conven~ional impact modifier and processing aid, provides the same impact strength and processability.
In general, the more co-impact modifier used, the greater the impact strength, and the cost-effectiveness of a co-modifier is evaluated by comparing impact strength versus parts of c~modifier per hundred parts of vinyl chloride resin matrix.
Any comparison of co-modifiers must take into account the fact that their rubber contents vary widely. Since improved impact strength is attributable to the weight percent (wt %) rubber, and the rubber contents vary, formulations are compared at constant wt % rubber, or constant parts rubber per hundred parts resin (phr), and the total weight of resin includes CPVC, polystyrene from the SBS
(say) ultra-modifier block copolymer used, and resin from grafted impact modifier.
In a first embodiment, the invention is concerned with the use of the SD or SDS linear or radial block copolymer as the only modifier, that is as a "pro-modifier", in commercially produced CPVC.
In a second embodiment, this invention is concerned with the use of the SD or SDS, linear or radial block copolymer conjointly with at least one other modifier, whqther an impact modifier or processing aid, or both, in commerciallyproduced CPVC. When plural modif{ers are used, one of which 1s the block copolymer, each of the rnodifiers includlng the block copolymer i9 referred to as a "co-modifier", and the effect on impact strength and processability of the combined co~modifiers may be, and generally is, unexpectedly more beneficial than their individual and separate, essentially merely additive effects. In this second embodiment of this invention, where a conventional impact modifier (a first co-modifer), is used with an SD or sbs block copolymer (as a second co-modifer), anincrease in impact strength is obtained which is unexpectedly greater than that obtained if the combined wt % rubber was present in the first co-modifier alone.Quite commonly a boost in impact strength is obtained with the two combined co-modifiers, despite the total wt % rubber therein being less than that necessary in a conventional impact modifier which produces comparable impact resistance. Total wt % rubber is the sum of the rubbery contents o~ the modifiers used, whether it be ,~ ,i ' ~' .
' ' the diene content of the block copolymer, or the diene or other similQr rubber content of a conventional c~modifier, in parts by weight per 100 parts by weightof CPVC composition.
There is provided in the first embodiment of this invention, an impact-modified thermoplastic composition free of conventional impact modifiers and processing aids, cs)mprising (a) a matrix comprising a chlorinated polyvinyl chloride polymer, and (b) a block copolymer pro-modifier consisting essentially of Q vinyl aromatic compound (S) and a conjugated diene (D) of the linear block, or radial block type, blocks ~D) being of either lower or higher average molecular weight than those of blocks (S), component (b) being present in an amount in the range from about 1 to about 10 wt %, and preferably from about 2 to about 8 wt % of the total resinous components of the composition. Component (b) is typically melt-Mended into the matrix and the CPVC blend so produced exhibits the same properties as conventionally modified CPVC blends, except that it has better processability and impact properties. The inherently excellent properties of CPVC, namely, low smoke, and low flammability, may now be obtained along with excellent impact strength and processability at lower cost than prior art CPVC
blends.
In general, the processability of polymers of halogenated vinyl monomers, and particularly PVC and CPVC, is so poor that processing aids must bemelt-blended into the matrix along with the impact modifier. Typically a processing aid is a random copolymer of styrene and acrylonitrile, or a copolymer of ~-methyl styrene and methyl methacrylate, or polymethylmethacrylate, any one or more o~ which is used in an amount less than about 10 % by wt, and preferably in an amount in the range from about 1% to about 5% by wt.
The preclse mechanism by which the presence of a small amount of pro-modifier, less than 10% by wt, contrlbutes to the Impact strength and processability of the CPVC, is unknown, but a mechanism is hypothesized. During molten polymer blending of the pro-modifier into the CPVC matrix, a broad distributIon of rubber particle sizes occurs. The pro-modifier contributes very small partlcles in the size range~from about 200 R to about 1000 Q (Angstrom ; ~ units), as well as some larger particles in the range from 1000 A to about 10,000 A.
` In particular, durlng melt blending, there is agglomeration of some rubber particles which further contributes to a broad particle size distribution in the composition.
35~ Further, the glass transition temperature Tg of the polybutadiene block in the block copolymer is subst&ntially lower than the Tg of conventional impact modifiers, and thus improves impact strength. Yet another factor contributing to :
.
' ~ ' the desirable imp~ct and processing qualities of the pro~modified CPVC may be the inclusion of polystyrene blocks in the dispersed polybutadiene rubber particles to increase the volume of rubbery particles.
The chlorinated polyvinyl chloride polymers (CPVC) used in this invention may be chlorinated homopolymers of vinyl chloride, or copolymers of chlorinated vinyl chloride and other monomers copolymeri~able therewith, and CPVC constitutes in excess of 50% by weight of the composition of this invention.
More preferably, the matrix of CPVC is present in the range from sbout 70% to about 95% by weight of the composition, the remainder being block copolymer pro-modifier. Other additives, not`uniformly distributed within the CPVC matrix, andnot used primarily for impact modification or processability, are disregarded for the purpose of this invention. Examples of other monomers referred to include vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, and the like; alpha-olefins, such as ethylene, propylene, butylene and the like; and alkyl acrylates or methacrylates having up to 18 carbon atoms in the alkyl moiety.
Preferred chlorinated polymers include polyvinyl chloride, and to the extent that they can be chlorinated, chlorinated vinyl chloride/vinyl acetate copolymers, and chlorinated vinyl chloride/ethylene copolymers, the former containing from about 5 to about 20% by weight of vinyl acetate, and the latter containing from about 0.3 to about 1.9% by weight ethylene copolymerized therein. Most preferred are general purpose types of commercially available CPVC produced as particularly described in U. S. patent No. 2,946,489.
Block copolymers of vinyl aromatic compounds and conjugated dienes are described in KeMedy et al., (Editor) 'tPolymer Chemistry of Synthetic Elastomer9", Interscience, Vol. 23, Part II, 1969, pages 533-559~ R. Zelinski and C.
W. Ch11ders "Rubber Chemistry and Technology" Vol. 41, page lB1 et seg. (1968);
;~ and "Technology" Vol. 43, page 22 et seq. (1970). The block copolymers are of the SD or SDS type in which the relative ratios of the homopolymer blocks can vary. In the compositions of this invention, the block copolymer's blocks D will always be those of R con~ugated diene, e.g., butadiene; isoprene; 1,3-pentadiene; 2,3-dimethyl-butadiene, and the like or mixtures of the foregoing; and blocks S willalways be derived from a vinyl aromatic compound, e.g., styrene, c~ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, or mixtures of any of the foregoing. In the~ most preferred compositions, the block copolymer pro-modifierwill ~have blocks S comprised of polystyrene, and blocks B comprised of polybutadiene.
The pro-modifier necessarily has either a linear block or a radial ~; teIeblock structure, "teleblock" being used to designate copolymers with terminal - , ' ,. ' '':
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block segments of one of the monomers used to produce them. Preferred are linearblocks having polyvinyl aromatic terminal blocks, and radial trichain and tetra-chain Mocks having polyvinyl aromatic terminal blocks. Of course, linear diblocks have terminal S and D blocks, and in all the SDS copolymers the terminal blocks will be vinyl aromatic, e.g., from styrene. ~'Radial" means a network in which the polystyrene blocks make the rubber thermoplastic tby virtue of the weight content) and association provides a network of plastic areas connected by flexible diene rubber blocks so the material has excellent mechanical properties without vulcanization. Although they are rubbery solids, the linear block and radial teleblock polymers soften and flow with heat and can be molded and extruded in the same manner as other thermoplastic materi~s. They can be remolded repeatedly without loss in properties. The precise structure of the block copolymer, that is, whether it is a diblock, triblock, or mixed polyblock copolymer is not critical, nor is its molecular weight, provided it is in the range specified hereinafter.
The ratio of the co-monomers can vary broadly, and the average molecular weight (mol wt) of combined blocks (D) may be either less than or greater than that of combined terminal blocks (S). It is preferred that the mol wt of combined blocks (D) be greater than the mol wt of combined blocks (S), to introduce desirable rubber into the composition. Higher rubber content is preferred if optimum impact strength is to be contributed by the pro-modifier. Thus, styrene-butadiene (SB) block copolymers are particularly useful and desirable since melt-blending and processing the components is relatively easy. Typically the average mol wt of the block copolymer is in the range from about 50,000 to about 25 300,000, and the average wt % of the combined vinyl aromatic terminal blocks (S) will range from about 20% to about 50%. In preferred block copolymers the aromatic compound units comprise a minor fraction by weight of the block copolymer,and the diene units the major fraction from about 60% to about 80%.
The block copolymers are made by an organolithium initiated polyme~
30 ization process in hydrocarbon solution using, for example, butadiene and styrene or other diene and vinyl aromatic monomers as is described in Kennedy et al, mentioned above.
, ; In one process, a SDS block copolymer is prepared by dissolving the conjugated diene, e.g., butadiene, in an aromatic hydrocarbon solvent, e.g., xylene, toluene, etc., and adding 0.3 to 7.5 millimoles/100 parts of monomer, of an organolithium initiator, e.g., n-butyl lithium, etc. Polymerization of the diene is aompleted and then the vinyl aromatic compound is added and polymerization of this is completed to form the block copolymer. The product is precipitated and deactivated, e.g., with alcohol, such as ethanol or isopropanol and purified by , ' ~. ' , ' ~
-.
-redissolving in hydrocarbon and reprecipitating with alcohol.
In another process, the block copolymer is formed using, e.g., a secondary or tertiary alkyl lithium compound at about 100-2,000 parts per million based on the total weight of the monomers and a polymerization temperature in the range from about 20C to about 65C. For example, sty-rene is dissolved in cyclohexane at 32C, and treated with 5,530 parts per million of secondary butyl lithium. After polymerization is complete, isoprene is injected and poly-merization is continued at 55C-57C. The product can be recovered as described above.
Monovinyl-substituted aromatic hydrocarbons and conjugated diene block copolymers are commercially avialable from Shell Chemical Company under the trademark KRATON.
These SDS block copolymers may be prepared by anionic solu-tion polymerization methods with organo-metallic catalysts as more fully described in U.S. Patent No. 3,265,765, and the Encyclopedia of Polymer Science and Technology, 15, pgs 508-530, Interscience Publishers, NYC (1971). The commonly used designations of SBS for styrene-butadiene-styrene and SIS for styrene-isoprene-styrene block copolymers, are used for bre~ity, in this specification.
Other commercially available SBS blockcopolymers are useful promodifers; for example, the block copolymer resins available as Solprene* rubbers, arld K-resins* KRO-l and KRO-3 from Phillips Petroleum Company, which resins are more fully di~closed in U.S. Patent No. 3,639,517 inter alia.
KRO-l contains about 73.6 wt percent of pure polystyrene blocks, balance polybutadiene blocks, the polybutadiene hav-ing a substantial percent of the cis-1,4-microstructure. The intrinsic viscosity in a typical ~ample is 0.67 dl/g (in chloroform at 25C). KRO-3 is a radial teleblock copolymer, like KRO-l, but the styrene content is about 75.8 wt percent and the intrinsic viscosity is slightly lower, about 0.64 dl/g. The glass transition point of the polybutadiene seg-ments in each case is about -90C. KRO-l shows a bimodal molecular weight distribution by gel phase chromatography.
KRO-3 has a smaller, low molecular weight peak.
A~ *Reg. U.S. Trademark .
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1~11177 ., -lla-The method of forming the polymer composition is not critical, prior art blending techniques being suitable.
The preferred method comprises melt blending the resinous components and additives in any of several ways, including providing the components in powder, granular, filamentous, or other convenient form, extruding the blend and chopping into pellets for molding to preselected shape by molding means conventionally used to mold normally solid thermo-plastic compositions. In some instances the components of the composition may be utilized as a blend of powders which blend may be directly formed into rigid shapes.
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for example, by extrusion.
The importance of the boost in impact properties contributed by a relatively small smount of SDS pro-modifier generally less than 10 wt % of the resinous components of the composition, is more particularly appreciated because5 the boost is achieved in conjunction with surprisingly good processability. Though, as with conventional impact modifiers and processing aids, particularly a processing aid such as CPE, there is some loss of room temperature tensile properties and HDT, but this loss is more acceptable.
In the second embodiment of this invention referred to hereinabove, 10 the CPVC matrix is conjointly modified by melt-blending with an SD or SDS block copolymer, and a conventional graft copolymer of the hard shell resin type.
Preferably, a processing aid is a~so melt-blended into the matrix. Since the block copolymer is now used in conjunction with conventional modifiers, it is now referred to as a co-modifier, as are the conventional impact modifier and 15 processing aid. In this embodiment, the composition comprises (a) a matrix comprising a chlorinated polyvinyl chloride polymer, (b) an SD or SD~ block copolymer co-modifier described hereinabove, and (c) a conventional impact modifier, component (b) being present in an amount in the range from about 1 to about 10 wt ~6, and preferably from about 2 to about 8 wt % of the total resinous 20 components of the composition, and component (c) being present in an amount in the range from about 1 to about 10 wt %, and preferably from about 2 to about 5 wt % of the total resinous components of the composition.
The contribution of the conventional impact modifier with respect to improving the impact strength is not critical. In general, when an SD or SDS blo~k 25 copolymer is used as a co-modifier with a conventional impact modifier such as a graft copolymer, and optionally, with a processing aid, the graft copolymer is present in the matrix in an amount sufficient to contribute substantial impact strength to the rigid CPVC. By "substantial" impact strength I refer to an increase in Izod impact strength of at least 20% oYer the impact strength of CPVC without30 an impact modifier.
In a CPVC composition including the block copolymer and another co-modifier, a synergistic effect is obtained as evidenced by an unexpected boost in impact strength of the melt-blended composition. Though the mechanism by which such a boost in impact strength is obtained is not clearly understood, it is 35 hypothesized that the block copolymer produces, during melt-blending, a broaddistribution of rubber particle sizes. This hypothesis is consistent with that ; proffered to explain the boost in impact strength of the block copolymer used as a pro-modifier. It is appreciated that distribution of rubber particle sizes over a wide range, by itself, does not offer a satisfactory explanation for the excellent , .. ... . . .. . ..
: ~ . .
- . . . -: - ~ . . . . -processability of CPVC modified with the block copolymer, and it may be that unidentified physico-chemical effects peculiar to the block copolymer play an essential role. The fact remains that the block copolymer produces impact strength and processability which is demonstrably far greater than one might 5expect for so small (low wt %) a contribution of rubber. For example by replacing from 20% to about 40% by wt of the rubber from a graft copolymer co-modifier, with rubber (butadiene) from an SB or SBS co-modifier, an unexpected boost in impact strength is obtained. It appears that the separate particles of block copolymer and graft copolymer, in conjunction with their chemical affinity to form 10large agglomerates, in addition to a wide size range of others, eccounts for the special effects attributable to the block copolymer.
Suitable graft copolymers are those conventionally used as impact modifiers for vinyl chloride polymers, and for the most part, commercially available graft copolymers are preferred. These graft copolymers chracteristically 15have a rubbery center upon which is graft copolymerized a shell of hard resin. The process for polymerization of the rubbery center and subsequent overpolymeriza-tion of the hard resin by graft copolymerization, is well known. Typical preferred graft copolymerized impact modifiers used for vinyl chloride polymers are those of the MBS type, commercially available as B~,A-III S and BTA III N from Kureha Co.;
20those of the ABS type, available as Blendex 301 and 311 from Marbon; and those of the PMMA/PBA type, available as KM323B from Rohm ~ Haas.
In each of the embodiments of the composition of this invention, at impact strain rates, the beneficial effect of the SDS or SD block copolymer is manifested in R lower yield stress (craze initiation) and in an increased elongation 25to break (plasticity). The net effect, assuming the optiumum amount i8 not exceeded, is that of adding more rubber as co-modifier without actually having done 90.
The boost in impact strength attributable to the SDS block copolymer is not Q transient effect such as sometimes results from frozen-in effects during 30rapid cooling. The impact strength and other desirable properties of the composition of this invention persist even after the composition is annealed below its Tg. The composition of this invention may be formulated in the same physicalmanncr, utilizing the same equipment, as known conventionally impact-modified chlorinated polyvinyl chloride polymers, but with appropriate changes in the recipes 35to compensate for the~ fact that the SDS or SD block copolymers generally soften ! `~ ~ and hasten fusion of the CPVC ingredients-It is of great commercial importance that hastening of fusion of CPVC
while melt-blending the block copolymer into the CPVC decreases the time .
. ~:: -, -, . .. . .
. - - - ,- - . . ., :
1~11177 required, yet the novel CPVC blend exhibits greater impact strength over a broader temperature range than do conventional CPVC blends.
The invention will be more fully understood and appreciated by the further description of the specific embodiments set forth in the examples which 5 follow. All parts and percentages refer to weight unless otherwise stated.
The îollowing recipes with ingredients as specified, are mechanically blended in a 4" Getty mill for about 4 minutes at about 200C, and compression-molded at about 215C in a l~boratory press.
In examples 1 - 5 set forth herein in Table I hereinbelow, GEON*603-10 x560 CPVC, available from The B.F.Goodrich Company, is master-batched with varying amounts of KRATON 1102 pro-modifier, which is a thermoplastic linear SBS block copolymer available from Shell Chemical Co. GEON 603x560 CPVC
contains from about 65.3% to about 65.9% bound chlorine, and has an inherent viscosity in the range from about 0.90 to about 0.95 in cyclohexanone. Each b~.tch of 100 parts of CPVC contains 1.125 parts lubricant, such as MICROTHENE 510 polyethelene; 2.0 parts stabilizer, such as T-31 THERMOLITl~tabilizer, which is a dibutyl tin bisisooctylthioglycollate. Each batch is milled at 200C for 4 minutes and compression molded into test pieces. The polyethylene lubricant provides lubricity and prevents sticking of the resin to the rolls. A lubricant does not function as a processing aid in that the lubricant does not aid fusion and does not substantially smoothen out or soften the stock. Pigments, such as TiO2 powder inthe form of rutile, if added, impart opacity to the blend and serve as a base for coloration. The Izod impact strength value tabulated for each example is the average of six test pieces. S8mples with no pro-modifier, that is, with zero rubber content, had an impact strength of 0.50 + 0.1 ft-lb/ln.
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~ 1111177 TABLE I
Ex.CPVC matrixPro-modifier Rubber Izod Std.
No.Geon 603x560Kraton 1102 content~* impact dev.
g g phr ft-lb/in ( +S ) 100 2.0 0.0 1.1 0.09
2 100 4.0 2.8 1.5 0.22
3 100 6.û ~.0 4.6 0.90 100 8.0 5.3 6.3 0.90 100 10.0 6.5 4.0 0.60 *~computed on the basis of Kraton 1102 containing 72% rubber.
The foregoing data demonstrates that the block copolymer pro-modifier produces a several-fold improvement in the impact strength of unmodified CPVC. These data are plotted in Figure 1 of the drawing, the parts of SBS per hundred parts resin along the abcissa, and impact strength along the ordinate. The curve indicates that a maximum impact strength is obtained at about 8 phr SBS for those test samples.
The following recipes yield CPVC compositions which demonstrate that a wide variety of commercially available block copolymers are excellent pro-modifiers, imparting substantially better impact strength than ahlorinated polyeth-ylene (CPE) which is the only known dual function modifier capable of providing acceptable melt-blended CPVC. The pro-modifiers used in compositions tested in Tabie II hereinbelow are identified as follows:
Chlorinated Polyethlene (CPE) used in Ex. 14 is available as LD-963 from duPont.KRA.TON~ 1101 Linear triblock SBS copolymer, 70% butadiene (Shell) SOLPRENE~ 406 radial block SBS copolymer, 60% butadiene (Philllps) SOLPRENE~ 414 radial block 8BS copolymer, 60% bu~adiene (Phillips) SOLPRENE~ 416 radial block SBS copolymer 70% butadiene (Phillips) SOLPRENE~ 422 radial block SBS copolymer, 80% butadiene (Philllps) SOLPRENE ~ 120S linear diblock SB copolymer, 75% butadiene (Phillips) Each batch is formulated with 100 parts GEON~ 605x560 CPVC and a small amount, less than 10 parts of pro-modifier which are melt-blended with 1 part MICROTHENE~510 and 2.0 partsT-31 THERMOLITE~ stabilizer. GEON~
605x560 CPVC contains abnut 65.7% bound chlorine and has an inherent viscosity of about~ 0.69 in cyclohexanone. Eaoh batch is milled at 200C for 2 minutes and compression molded into test pieces. Izod impact strengths tabulated are the averages of six test samples.
Registered U.S. Trademark ., . .. . , - .
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TABLE II
Ex.CPVC matrixPro-modifier Izod Std.
No.Geon 605x560 identif.~ wt. impact dev.
g(name) gft-lb/in ( +S ) 6100Kratonl102 6.0 1.20 0.29 7100KratonllO1 7.5 1.64 0.47 8100KratonllOl 9.0 1.58 0.26 9100Solprene406 7.5 1.63 0.25 10100Solprene414 7.5 1.63 0.25 11100Solprene416 7.5 1.49 0.38 12100Solprene422 7.5 2.15 0.60 13100Solprenel205 7.5 2.02 0.32 14100CPE,LD-963 7.5 0.69 0.13 In the following recipes, mixed linear and radial pro-modifier~ are used to provide a CPVC with tailored impact and processability characteristics. (All batches are ~ormulated with 100 parts GEON~ 603x560 CPVC which is melt-blended on a mill with the pro-modifier, 1.125 parts MICROTHENE* 510 lubricant 5 and 2.0 parts T-31 THERMOLITE* stabilizer.) As will be evident from the data in Table III hereinbelow, longer milling conditions at higher temperatures seriously impair impact strength. This appears to be clearly evident for individual lineartriblocks, and also for individual radial blocks of SBS. When the linear and radial blocks are mixed, the effect of the higher temperature milling for longer time is 10 less noticeable. As in the foregolng examples, lzod impact strength values tabulated are the average of six compression molded test samples.
TABLE III
Ex.Pro-modlfier Pro-modifier Milling Milling Izod Std.
No.identificationweight TeOmp. Time impact Dev.
;; g C min ft-lb/in (~S) 15Kraton*1101 6 200 2 7.0 1.3 16Kraton~llO1 6 220 4 3.0 0.3 17Kraton~1102 6 200 2 3.8 1 ~ 5 18Kraton~1102 6 220 4 2.7 0.4 19Solprene~416 6 220 2 8.7 1.1 20Solprene*416 6 220 4 1.8 002 21Solprene~422 6 220 4 1.1 0.2 23Kraton~1102 ~ 4 200 2 7.5 0.8 Solprene~416 2 a4Kraton*1102 ~c 4 220 4 5.7 1.1 Solprene~416 2 * Registered U.S.Trademark ..
- . .
.
1~11177 In the following recipes a thermoplastic linear triblock SBS block copolymer available as KRATON 1102 from Shell Chemical Co. is compared, on an equal weight basis, with LD-963 solution chlorinated CPE availQble from duPont and an MBS type co-modifier available as ~TAIIIN available from Kureha Co. Each 5 batch was mixed on a 6 in diameter mill using 500 g of CPVC, with 30 g of co-modifier, 5.63 g of polyethylene lubricant and 10 g of a tin stabilizer. All batches were blended at 205C, roll temperature, for 5 minutes after banding.
The melt index of each batch is measured with a Monsanto Capillary Rheometer. The lower the value, the poorer is the flow of extruded melt. Higher 10 values indicate good flow of extruded melt, and good flow directly results in a time saving when formulating a master batch.
Mill shrinkage is a reflection of melt elasticity and is evidenced by lateral and longitudinal shrinkage of a melt-blended section of sheet as soon as the section is cut from stock on the mill, and allowed to cool.
The heat distortion temperature (HDT) is measured at 264 psi utilizing 0.125 in thick samples. It will be evident that the inclusion of pro-modifier in the CPVC does not significantly alter the HDT of a conventional CPVC composition.
The values tabulated for Izod impact of samples molded from various recipes set forth in Table IV hereinbelow, are average values of six compression20 molded samples, and all failures were of the ductile type.
TABLE IV
Ex.Modifier Melt Mill HDT Izod No.Identlfication IndexShrinkage impact % C ft-lb/in CPE 0.507513 103.5 4.20 2ffBTAXIIN 0.188212 102.5 3.93 27Kraton 1102 0.4553 9 105.0 6.25 The foregoing results show that CPVC with Kraton 1102 pro-modifier 30 has essentially the same HDT as CPVC with either CPE or BTAIIIN, but the millshrinkage and impact strength of CPVC with Kraton 1102 are each better than that of either of the other compositions, and the melt index of CPVC with Kraton1102 is close to that of CPVC with CPE.
In a manner analogous to that in which each of the batches of 35 examples 25-27 ~re blended, additional batches having the same compositions are prepared except that the blending time after banding on 205C rolls is limited to 2 min, whioh is one-half the blending time provided in the aforementioned examples.
Some of the physical properties of the batches blended for only 2 min are set forth in Table V hereinbelow.
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TABLE V
Ex. Modifer Melt Mill HpT Izod No.Identification Index Shrinkage O impact % C ft-lb/in 28 CPVC 0.4456 10.4 106.5 a.70 29 BTAIIIN O .1649 13 . 0 105 . 5 3 . 28 KratonllO2 1.3592 8.4 105.5 5.87 The foregoing results show that CPVC with Kraton 1102 pro-modifier, melt-blended for 2 min. at 205C roll temperature, has essentia~y the same HDT
as CPVC with either CPE or BTAIIIN, but the melt index, mill shrinkage and impact strength of CPVC with Kraton 1102 are each better than that of either of the other 5 compositions. It is especially noteworthy and surprising that the melt index of CPVC with Kraton 1102 is much better than that of CPVC with CPE with the shorter blending time. Clearly, the particular conditions of processing CPVC andpro-modifier to yield the composition of this invention, affects the physical properties of the composition. The most desirable processing conditions for a 10 particular pro-modified CPVC may be obtained by simple trial and error. It ispresumed that the processing conditions affect the degree of dispersion as well as the particle~ size distribution of the pro-modifier in the CPVC matrix, and neither is predictable.
The foregoing examples illustrate the effect of an SB or SBS block co-15 polymer, or mixtures thereof, as the sole pro-modifier in CPVC. As has been stated hereinabove, an SBS or SB pro-modifier may be used as a co-modifier in combination with conventional impact modifiers to tailor the physical properties of the modi$1ed CPVC composition. Though the effect of block co-polymer in ~uch a combination varles widely depending upon the type of blook co-polymer ¢hosen, the 20 impact strength of the combination of ¢o-modlflers, when evaluated on the basis of their rubber content (% by wt), is greater than the impact strength attributable to ~ ~ ~ the same rubber content in a conventional gra$ted co-modifier. Such an ;~ ~ unexpeoted improvement in Impact strength is also obtained when CPVC is co-modified with a combination of SB or SBB block c~polymer co-modifier, and a cpe 2S co-modifier which i9 an ungrafted impact modifier.
In the Iollowing examples 31-34 set forth in Table Vl hereinbelow, GEON 603x560 CPVC is compounded to contain 6.0% by wt total rubber. In ; ~ ; example~31 only, BTAIIIN, which is an MBS type of graft co-polymer, is used as the co-modifier.~ ln example 34, only Kraton 1102 which is a thermopl~stic SBS linear 30 ~ block c~polymer, is used as the co-modifier. In examples 32 ~nd 33 each co-modiflér contributes a portion of the rubber content. A~ in the previous examples, eaeh batch~ is ~compounded with MICROTHENE polyethylene lubricant (0.5 phr), ,, ~ .
THERMOLITE T-31 stabilizer (2.5 phr), and some finely divided filler such as TiO2, preferably in the uncoated rutile form. The components are melt-blended between 205C rolls for 2 min after banding. The values tabulated for Izod impact strength are the average values of six samples compression molded at 210C.
TABLE Vl Ex.CPVC matrixCo-modifierCo-modifier Izod Std.% rubber No.GEON 603x560BTAIIINKraton 1102 impact dev.from SBS
g g g ft-lb/in ( +S) 31 100 8.5 0.0 2.5 0.4 0.0 3299.5 4.2 4.8 9.6 1.6 25.0 3399.2 2.1 7.2 3.3 0.6 75.0 3498.9 0.0 9.6 1.9 0.3 100.0 The foregoinE results show that the impact strength is higher when the rubber content of the composition is contributed by each c~modifier, rather thanby either one by itself. Figure 2 is a plot of Izod impact strength for the samples tested, the results of which are tabulated in Table VI hereinabove, showing graphically the synergistic effect of the contribution of rubber from SBS to theimpact strength of the molded test strips.
In a manner analogous to that in which each of the batches of Examples 31-34 are melt-blended, GEON 603x560 CPVC is modified individu~lly and conjointly with with KRATON 1102 SBS linear block co~olymer and KM323B
which is a grafted PMMA/PBA type (66% polybutyl acrylate rubber coated with polymethyl/methacrylate) OI co-polymer available from Rohm ~ Haas. Each batch ls formulated by melt-blending 100 g GEON 603x560 CPVC with MICROTHENE
polyethylene lubricant (1.5 g), THERMOLITE T-31 stabilizer ~2.0 g) and TiO2 uncoated rutile (2.0 g). The components are melt-blended between 210C roll~ for2 mln after banding. The values tabulated for Izod Impact strength are the average ; 25 values of six samples compression molded at 210C. The results obtained are set ; ~ forth in Table Vll hereinbelow.
TABLE Vll EX.CPVC matrix Co-modifier Co-modifier Izod Std.
No.GEON ffO3x5B0 KM323B KratonllO2 impact dev.
g g g ft-lb/in ( S) 35 100 4 0 0.79 0.23 36 100 3 1 l.a7 0.18 37 100 2 2 1.41 0.1a 38 100 1 3 1.74 o.a6 39 100 0 4 1.94 0.33 ,~ . , , : i -. . . ,. ~ - :. .. .. . . .
. - , , - ~ - ~ . -In a manner analogous to that in which each of the batches of Examples 35-39 are blended, KRO-3 polymer which is a plastic radial SBS block copolymer and an ungrafted CPE are melt-blended individually and conjointly as co-modifiers, and the results obtained are set forth in Table VIII hereinbelow. Each 5 batch is formulated by melt-blending about 100 g (adjusted as stated) of GEON
603x560 CPVC and enough co-modifier(s) to provide 4 phr rubber in the composition. When KRO-3 SBS block copolymer is mixed with CPE the rubber content is maintained at 4 phr, and the % of rubber contributed by the SBS blockcopolymer is recorded. Additionally, each batch includes MICROTHENE polyethyl-ene lubricant (1.5 g), THERMOLITE T-31 stabilizer (2.5 g) and TiO2 filler (5.0 g).
The components are melt-blended between 205C rolls for 2 min after banding~
The values tabulated for Izod impact strength are the average values of six samples compression molded at 210C.
TABLE VIII
Ex. CPVC matrixCo-modifierCo-modifierRubber Izod Std.
No.GEON603x560 CPE KRO-3 fromSBS impact ( +S) 100 4.0 0.0 0.0 0.58 0.20 41 98.3 3.5 2.a 12.5 0.78 0.19 42 96.6 3.0 4.4 25.0 1.50 0.13 43 95.0 2.5 6.5 37.5 1.21 0.34 Tn a manner analogous to that in which each of the b~tches of examples 40-43 are blended, additional batches are formulated except that the rubber content is maintained at 6 phr. The results are set forth in Table IX
hereinbelow.
TA.BLE IX
Ex.CPVC matrixCo-modifier Co-modifier Rubber Izod Std.
No.GEON603x560 CPE KR~3 ~rom SBS impact dev.
g g g % ~t-lb/in ( +S) 44 100 6.0 0.0 0.0 0.85 0.19 45 96.6 5.0 4.4 17. 1.77 0.38 46 93.3 4.0 8.7 33. 1.06 0.47 47 90.0 3.0 13.1 50. 0.64 0.09 In a manner analogous to that in which each of the batches of Examples 35-39 hereinabove are blended, 5 phr Kraton 1102 polymer, which is a linear block SBS copolymer, is combined for its effect, with various levels of Zerlon~ 150-Z27 modifier. Zerlon is not a conventional impact modifier as it contains no rubberj but it is methyl methacrylate/styrene (B5/35) copolymer Registered U.S. Trademark .
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' ' ' , : : . . -.---21--available from Dow Chemical Co. Lubricant and stabilizer are added as above, and the components melt-blended between 200C rolls for 120 sec after banding. Test pieces are compression molded at 210C, and the values set forth are the averages for six samples.
TABLE X
Ex. CPVC matrix Pro-modifierCo-modifier Izod Std No.GEON 603x560Kraton 1102 Zerlon 150-Z27 impact dev g g g ft-lb~in ( +S ) 48 100 5 0 2.70 0.34 49 97 5 3 3 . 10 1 . 0 94 5 6 a.42 0.38 51 gl 5 9 1 . 85 0 . 39 In any of the foregoing examples, SB diblock or SBS polyblock copolymers, whether linear or radial, may be used in mixed form or individually.When mixed, the r~tio of diblock to SBS polyblock, or the ratio of SBS linear polyblock to radi~l polyblock, or the ratio of any combinations thereof, may be varied to produce a resin of desirable optical and other physical characteristics 15 amongst which impact strength may be tailored for a particular purpose. Similarly, more than one co-modifier may be used in combination with a SB or SBS block copolymer modifier in which the particle sizes and molecular weights are varied,allowing an additional degree of latitude in tailoring a resin for further desirable physical characteristics and desired impact performance.
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:' .. ' . ' .. , . ' ., . ', . . '. .. , ': ' : ' .. : . ' . .' : ' ' ', '. , ' ' :' ' ' ' ~ ' ' ' ' ' ' ' ' ' . ' " . " ' . ' ' .
The foregoing data demonstrates that the block copolymer pro-modifier produces a several-fold improvement in the impact strength of unmodified CPVC. These data are plotted in Figure 1 of the drawing, the parts of SBS per hundred parts resin along the abcissa, and impact strength along the ordinate. The curve indicates that a maximum impact strength is obtained at about 8 phr SBS for those test samples.
The following recipes yield CPVC compositions which demonstrate that a wide variety of commercially available block copolymers are excellent pro-modifiers, imparting substantially better impact strength than ahlorinated polyeth-ylene (CPE) which is the only known dual function modifier capable of providing acceptable melt-blended CPVC. The pro-modifiers used in compositions tested in Tabie II hereinbelow are identified as follows:
Chlorinated Polyethlene (CPE) used in Ex. 14 is available as LD-963 from duPont.KRA.TON~ 1101 Linear triblock SBS copolymer, 70% butadiene (Shell) SOLPRENE~ 406 radial block SBS copolymer, 60% butadiene (Philllps) SOLPRENE~ 414 radial block 8BS copolymer, 60% bu~adiene (Phillips) SOLPRENE~ 416 radial block SBS copolymer 70% butadiene (Phillips) SOLPRENE~ 422 radial block SBS copolymer, 80% butadiene (Philllps) SOLPRENE ~ 120S linear diblock SB copolymer, 75% butadiene (Phillips) Each batch is formulated with 100 parts GEON~ 605x560 CPVC and a small amount, less than 10 parts of pro-modifier which are melt-blended with 1 part MICROTHENE~510 and 2.0 partsT-31 THERMOLITE~ stabilizer. GEON~
605x560 CPVC contains abnut 65.7% bound chlorine and has an inherent viscosity of about~ 0.69 in cyclohexanone. Eaoh batch is milled at 200C for 2 minutes and compression molded into test pieces. Izod impact strengths tabulated are the averages of six test samples.
Registered U.S. Trademark ., . .. . , - .
~.
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:, .: , - . . . . . .
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TABLE II
Ex.CPVC matrixPro-modifier Izod Std.
No.Geon 605x560 identif.~ wt. impact dev.
g(name) gft-lb/in ( +S ) 6100Kratonl102 6.0 1.20 0.29 7100KratonllO1 7.5 1.64 0.47 8100KratonllOl 9.0 1.58 0.26 9100Solprene406 7.5 1.63 0.25 10100Solprene414 7.5 1.63 0.25 11100Solprene416 7.5 1.49 0.38 12100Solprene422 7.5 2.15 0.60 13100Solprenel205 7.5 2.02 0.32 14100CPE,LD-963 7.5 0.69 0.13 In the following recipes, mixed linear and radial pro-modifier~ are used to provide a CPVC with tailored impact and processability characteristics. (All batches are ~ormulated with 100 parts GEON~ 603x560 CPVC which is melt-blended on a mill with the pro-modifier, 1.125 parts MICROTHENE* 510 lubricant 5 and 2.0 parts T-31 THERMOLITE* stabilizer.) As will be evident from the data in Table III hereinbelow, longer milling conditions at higher temperatures seriously impair impact strength. This appears to be clearly evident for individual lineartriblocks, and also for individual radial blocks of SBS. When the linear and radial blocks are mixed, the effect of the higher temperature milling for longer time is 10 less noticeable. As in the foregolng examples, lzod impact strength values tabulated are the average of six compression molded test samples.
TABLE III
Ex.Pro-modlfier Pro-modifier Milling Milling Izod Std.
No.identificationweight TeOmp. Time impact Dev.
;; g C min ft-lb/in (~S) 15Kraton*1101 6 200 2 7.0 1.3 16Kraton~llO1 6 220 4 3.0 0.3 17Kraton~1102 6 200 2 3.8 1 ~ 5 18Kraton~1102 6 220 4 2.7 0.4 19Solprene~416 6 220 2 8.7 1.1 20Solprene*416 6 220 4 1.8 002 21Solprene~422 6 220 4 1.1 0.2 23Kraton~1102 ~ 4 200 2 7.5 0.8 Solprene~416 2 a4Kraton*1102 ~c 4 220 4 5.7 1.1 Solprene~416 2 * Registered U.S.Trademark ..
- . .
.
1~11177 In the following recipes a thermoplastic linear triblock SBS block copolymer available as KRATON 1102 from Shell Chemical Co. is compared, on an equal weight basis, with LD-963 solution chlorinated CPE availQble from duPont and an MBS type co-modifier available as ~TAIIIN available from Kureha Co. Each 5 batch was mixed on a 6 in diameter mill using 500 g of CPVC, with 30 g of co-modifier, 5.63 g of polyethylene lubricant and 10 g of a tin stabilizer. All batches were blended at 205C, roll temperature, for 5 minutes after banding.
The melt index of each batch is measured with a Monsanto Capillary Rheometer. The lower the value, the poorer is the flow of extruded melt. Higher 10 values indicate good flow of extruded melt, and good flow directly results in a time saving when formulating a master batch.
Mill shrinkage is a reflection of melt elasticity and is evidenced by lateral and longitudinal shrinkage of a melt-blended section of sheet as soon as the section is cut from stock on the mill, and allowed to cool.
The heat distortion temperature (HDT) is measured at 264 psi utilizing 0.125 in thick samples. It will be evident that the inclusion of pro-modifier in the CPVC does not significantly alter the HDT of a conventional CPVC composition.
The values tabulated for Izod impact of samples molded from various recipes set forth in Table IV hereinbelow, are average values of six compression20 molded samples, and all failures were of the ductile type.
TABLE IV
Ex.Modifier Melt Mill HDT Izod No.Identlfication IndexShrinkage impact % C ft-lb/in CPE 0.507513 103.5 4.20 2ffBTAXIIN 0.188212 102.5 3.93 27Kraton 1102 0.4553 9 105.0 6.25 The foregoing results show that CPVC with Kraton 1102 pro-modifier 30 has essentially the same HDT as CPVC with either CPE or BTAIIIN, but the millshrinkage and impact strength of CPVC with Kraton 1102 are each better than that of either of the other compositions, and the melt index of CPVC with Kraton1102 is close to that of CPVC with CPE.
In a manner analogous to that in which each of the batches of 35 examples 25-27 ~re blended, additional batches having the same compositions are prepared except that the blending time after banding on 205C rolls is limited to 2 min, whioh is one-half the blending time provided in the aforementioned examples.
Some of the physical properties of the batches blended for only 2 min are set forth in Table V hereinbelow.
. . , . -..
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.
TABLE V
Ex. Modifer Melt Mill HpT Izod No.Identification Index Shrinkage O impact % C ft-lb/in 28 CPVC 0.4456 10.4 106.5 a.70 29 BTAIIIN O .1649 13 . 0 105 . 5 3 . 28 KratonllO2 1.3592 8.4 105.5 5.87 The foregoing results show that CPVC with Kraton 1102 pro-modifier, melt-blended for 2 min. at 205C roll temperature, has essentia~y the same HDT
as CPVC with either CPE or BTAIIIN, but the melt index, mill shrinkage and impact strength of CPVC with Kraton 1102 are each better than that of either of the other 5 compositions. It is especially noteworthy and surprising that the melt index of CPVC with Kraton 1102 is much better than that of CPVC with CPE with the shorter blending time. Clearly, the particular conditions of processing CPVC andpro-modifier to yield the composition of this invention, affects the physical properties of the composition. The most desirable processing conditions for a 10 particular pro-modified CPVC may be obtained by simple trial and error. It ispresumed that the processing conditions affect the degree of dispersion as well as the particle~ size distribution of the pro-modifier in the CPVC matrix, and neither is predictable.
The foregoing examples illustrate the effect of an SB or SBS block co-15 polymer, or mixtures thereof, as the sole pro-modifier in CPVC. As has been stated hereinabove, an SBS or SB pro-modifier may be used as a co-modifier in combination with conventional impact modifiers to tailor the physical properties of the modi$1ed CPVC composition. Though the effect of block co-polymer in ~uch a combination varles widely depending upon the type of blook co-polymer ¢hosen, the 20 impact strength of the combination of ¢o-modlflers, when evaluated on the basis of their rubber content (% by wt), is greater than the impact strength attributable to ~ ~ ~ the same rubber content in a conventional gra$ted co-modifier. Such an ;~ ~ unexpeoted improvement in Impact strength is also obtained when CPVC is co-modified with a combination of SB or SBB block c~polymer co-modifier, and a cpe 2S co-modifier which i9 an ungrafted impact modifier.
In the Iollowing examples 31-34 set forth in Table Vl hereinbelow, GEON 603x560 CPVC is compounded to contain 6.0% by wt total rubber. In ; ~ ; example~31 only, BTAIIIN, which is an MBS type of graft co-polymer, is used as the co-modifier.~ ln example 34, only Kraton 1102 which is a thermopl~stic SBS linear 30 ~ block c~polymer, is used as the co-modifier. In examples 32 ~nd 33 each co-modiflér contributes a portion of the rubber content. A~ in the previous examples, eaeh batch~ is ~compounded with MICROTHENE polyethylene lubricant (0.5 phr), ,, ~ .
THERMOLITE T-31 stabilizer (2.5 phr), and some finely divided filler such as TiO2, preferably in the uncoated rutile form. The components are melt-blended between 205C rolls for 2 min after banding. The values tabulated for Izod impact strength are the average values of six samples compression molded at 210C.
TABLE Vl Ex.CPVC matrixCo-modifierCo-modifier Izod Std.% rubber No.GEON 603x560BTAIIINKraton 1102 impact dev.from SBS
g g g ft-lb/in ( +S) 31 100 8.5 0.0 2.5 0.4 0.0 3299.5 4.2 4.8 9.6 1.6 25.0 3399.2 2.1 7.2 3.3 0.6 75.0 3498.9 0.0 9.6 1.9 0.3 100.0 The foregoinE results show that the impact strength is higher when the rubber content of the composition is contributed by each c~modifier, rather thanby either one by itself. Figure 2 is a plot of Izod impact strength for the samples tested, the results of which are tabulated in Table VI hereinabove, showing graphically the synergistic effect of the contribution of rubber from SBS to theimpact strength of the molded test strips.
In a manner analogous to that in which each of the batches of Examples 31-34 are melt-blended, GEON 603x560 CPVC is modified individu~lly and conjointly with with KRATON 1102 SBS linear block co~olymer and KM323B
which is a grafted PMMA/PBA type (66% polybutyl acrylate rubber coated with polymethyl/methacrylate) OI co-polymer available from Rohm ~ Haas. Each batch ls formulated by melt-blending 100 g GEON 603x560 CPVC with MICROTHENE
polyethylene lubricant (1.5 g), THERMOLITE T-31 stabilizer ~2.0 g) and TiO2 uncoated rutile (2.0 g). The components are melt-blended between 210C roll~ for2 mln after banding. The values tabulated for Izod Impact strength are the average ; 25 values of six samples compression molded at 210C. The results obtained are set ; ~ forth in Table Vll hereinbelow.
TABLE Vll EX.CPVC matrix Co-modifier Co-modifier Izod Std.
No.GEON ffO3x5B0 KM323B KratonllO2 impact dev.
g g g ft-lb/in ( S) 35 100 4 0 0.79 0.23 36 100 3 1 l.a7 0.18 37 100 2 2 1.41 0.1a 38 100 1 3 1.74 o.a6 39 100 0 4 1.94 0.33 ,~ . , , : i -. . . ,. ~ - :. .. .. . . .
. - , , - ~ - ~ . -In a manner analogous to that in which each of the batches of Examples 35-39 are blended, KRO-3 polymer which is a plastic radial SBS block copolymer and an ungrafted CPE are melt-blended individually and conjointly as co-modifiers, and the results obtained are set forth in Table VIII hereinbelow. Each 5 batch is formulated by melt-blending about 100 g (adjusted as stated) of GEON
603x560 CPVC and enough co-modifier(s) to provide 4 phr rubber in the composition. When KRO-3 SBS block copolymer is mixed with CPE the rubber content is maintained at 4 phr, and the % of rubber contributed by the SBS blockcopolymer is recorded. Additionally, each batch includes MICROTHENE polyethyl-ene lubricant (1.5 g), THERMOLITE T-31 stabilizer (2.5 g) and TiO2 filler (5.0 g).
The components are melt-blended between 205C rolls for 2 min after banding~
The values tabulated for Izod impact strength are the average values of six samples compression molded at 210C.
TABLE VIII
Ex. CPVC matrixCo-modifierCo-modifierRubber Izod Std.
No.GEON603x560 CPE KRO-3 fromSBS impact ( +S) 100 4.0 0.0 0.0 0.58 0.20 41 98.3 3.5 2.a 12.5 0.78 0.19 42 96.6 3.0 4.4 25.0 1.50 0.13 43 95.0 2.5 6.5 37.5 1.21 0.34 Tn a manner analogous to that in which each of the b~tches of examples 40-43 are blended, additional batches are formulated except that the rubber content is maintained at 6 phr. The results are set forth in Table IX
hereinbelow.
TA.BLE IX
Ex.CPVC matrixCo-modifier Co-modifier Rubber Izod Std.
No.GEON603x560 CPE KR~3 ~rom SBS impact dev.
g g g % ~t-lb/in ( +S) 44 100 6.0 0.0 0.0 0.85 0.19 45 96.6 5.0 4.4 17. 1.77 0.38 46 93.3 4.0 8.7 33. 1.06 0.47 47 90.0 3.0 13.1 50. 0.64 0.09 In a manner analogous to that in which each of the batches of Examples 35-39 hereinabove are blended, 5 phr Kraton 1102 polymer, which is a linear block SBS copolymer, is combined for its effect, with various levels of Zerlon~ 150-Z27 modifier. Zerlon is not a conventional impact modifier as it contains no rubberj but it is methyl methacrylate/styrene (B5/35) copolymer Registered U.S. Trademark .
~': ' ' ,,, , ~ . ~ , ,, .
.
' ' ' , : : . . -.---21--available from Dow Chemical Co. Lubricant and stabilizer are added as above, and the components melt-blended between 200C rolls for 120 sec after banding. Test pieces are compression molded at 210C, and the values set forth are the averages for six samples.
TABLE X
Ex. CPVC matrix Pro-modifierCo-modifier Izod Std No.GEON 603x560Kraton 1102 Zerlon 150-Z27 impact dev g g g ft-lb~in ( +S ) 48 100 5 0 2.70 0.34 49 97 5 3 3 . 10 1 . 0 94 5 6 a.42 0.38 51 gl 5 9 1 . 85 0 . 39 In any of the foregoing examples, SB diblock or SBS polyblock copolymers, whether linear or radial, may be used in mixed form or individually.When mixed, the r~tio of diblock to SBS polyblock, or the ratio of SBS linear polyblock to radi~l polyblock, or the ratio of any combinations thereof, may be varied to produce a resin of desirable optical and other physical characteristics 15 amongst which impact strength may be tailored for a particular purpose. Similarly, more than one co-modifier may be used in combination with a SB or SBS block copolymer modifier in which the particle sizes and molecular weights are varied,allowing an additional degree of latitude in tailoring a resin for further desirable physical characteristics and desired impact performance.
`' ' ' ', , .
' ` ~ ' , ' " .' ' ' ' ' ' ' . '' ''' .' , ', ' .' :
:' .. ' . ' .. , . ' ., . ', . . '. .. , ': ' : ' .. : . ' . .' : ' ' ', '. , ' ' :' ' ' ' ~ ' ' ' ' ' ' ' ' ' . ' " . " ' . ' ' .
Claims (18)
1. A normally rigid thermoplastic composition comprising (a) a matrix comprising a chlorinated vinyl chloride resin, and (b) a dual function processing aid and impact modifier, or pro-modifier, consisting essentially of a block copolymer of a vinyl aromatic compound (S) and a conjugated diene (D), wherein said vinyl aromatic compound (S) is selected from the group consisting of styrene, .alpha.-methyl styrene, vinyl toluene, vinyl xylene, and naphthalene, said conjugated diene (D) is selected from the group consisting of butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl butadiene, and said pro-modifier is present in an amount in the range from about 1 percent to about 10 percent by weight based on the total resinous components of said composition.
2. The composition of Claim 1 wherein said chlorinated vinyl chloride resin is selected from the group consisting of copolymers of chlorinated vinyl chloride and a homopolymer of chlorinated vinyl chloride.
3. The composition of Claim 2 wherein said homopolymer of chlorinated vinyl chloride has at least 60% by weight chemically bound chlorine.
4. The composition of Claim 3 wherein said pro-modifier is present in an amount in the range from about 2 percent to about 8 percent by weight.
5. The composition of Claim 4 wherein said block copolymer pro-modifier has a structure selected from a polyblock structure including a linear diblock, linear triblock, and a radial teleblock structure.
6. The composition of Claim 5 wherein said chlorinated vinyl chloride polymer has primary resin particles in the size range from about 2500 .ANG. to about 2µ
(microns), and said block copolymer pro-modifier has primary particles in the size range from about 200 .ANG. to about 1µ .
(microns), and said block copolymer pro-modifier has primary particles in the size range from about 200 .ANG. to about 1µ .
7. The composition of Claim 6 wherein said pro-modifier includes vinyl aromatic compound units which comprise from about 20 to about 80 percent by weight of said block copolymer pro-modifier.
8. The composition of Claim 5, including in addition, at least one conventional impact modifier, or co-modifier, selected from the group consisting of an ungrafted chlorinated polyethylene and a grafted interpolymerization product of a hard resin and a rubbery polymer, wherein said hard resin is derived from a monounsaturated monomer, said pro-modifier and said conventional impact modifier being co-modifiers in said composition.
9. The composition of Claim 8 wherein said matrix is present in an amount in excess of about 85 percent by weight of the total resinous components in said composition and said co-modifiers together provide less than 10 parts rubber per 100 parts resinous components in said composition.
10. The composition of Claim 8 wherein each said co-modifier is present in an amount less than about 10% by weight of the total resinous components.
11. The composition of Claim 10 wherein said conventional impact modifier is selected from the group consisting of graft copolymerized impact modifiers of the MBS type, the ABS type and the PMMA/PBA type.
12. The composition of Claim 7 including in addition, a minor quantity in the range from about 1% to about 20% by weight of an interpolymer having no rubber content.
13. The composition of Claim 12 wherein said interpolymer is selected from the group consisting of copolymers of an alkyl methacrylate and styrene, and homopolymers and copolymers of vinyl chloride.
14. A reinforced composition as defined in Claim 1 including a reinforcing amount of fibrous glass.
15. A reinforced composition as defined in Claim 8 including a reinforcing amount of fibrous glass.
16. A method for preparing a normally rigid thermoplastic article comprising melt-blendlng (a) a chlorinated vinyl chloride resin having at least 60%
by weight bound chlorine, and (b) a block copolymer pro-modifier consisting essentially of a block copolymer of a vinyl aromatic compound (S) and a conjugated diene (D), wherein said vinyl aromatic compound (S) is selected from the group consisting of styrene, alpha-methyl styrene, vinyl toluene, vinyl xylene, and vinyl naphthalene, said conjugated diene (D) is selected from the group consisting of butadiene, isoprene, 1,2-pentadiene, and 2,3-dimethyl butadiene, and wherein said block copolymer pro-modifier is present in an amount in the range from about 1 percent to about 10 percent by weight, based on the total resinous components ofsaid composition, to obtain a uniform melt; and, shaping said melt to form said article.
by weight bound chlorine, and (b) a block copolymer pro-modifier consisting essentially of a block copolymer of a vinyl aromatic compound (S) and a conjugated diene (D), wherein said vinyl aromatic compound (S) is selected from the group consisting of styrene, alpha-methyl styrene, vinyl toluene, vinyl xylene, and vinyl naphthalene, said conjugated diene (D) is selected from the group consisting of butadiene, isoprene, 1,2-pentadiene, and 2,3-dimethyl butadiene, and wherein said block copolymer pro-modifier is present in an amount in the range from about 1 percent to about 10 percent by weight, based on the total resinous components ofsaid composition, to obtain a uniform melt; and, shaping said melt to form said article.
17. The method of Claim 16 comprising in addition, melt-blending into said melt at least one conventional impact modifier selected from the group consisting of an ungrafted chlorinated polyethylene and a grafted interpolymerization product of a hard resin and a rubbery polymer, wherein said hard resin is derived from amono-unsaturated monomer, said pro-modifier and conventional impact modifer being co-modifiers in said composition.
18. The method of claim 16 comprising in addition, melt-blending into said melt a minor quantity by weight of a synthetic resinous interpolymer containing no rubbery polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/889,458 US4181644A (en) | 1978-03-23 | 1978-03-23 | Impact modified polymer composition |
| US889,458 | 1978-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111177A true CA1111177A (en) | 1981-10-20 |
Family
ID=25395137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA321,405A Expired CA1111177A (en) | 1978-03-23 | 1979-02-13 | Impact modified polymer composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4181644A (en) |
| EP (1) | EP0004547B1 (en) |
| JP (1) | JPS54131653A (en) |
| AU (1) | AU526198B2 (en) |
| CA (1) | CA1111177A (en) |
| DE (1) | DE2962265D1 (en) |
| NZ (1) | NZ189648A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910007599B1 (en) * | 1983-01-27 | 1991-09-28 | 세끼스이 가세이힌 고오교오 가부시끼가이샤 | Granular organohalide flame retardant additive |
| US4530968A (en) * | 1984-06-19 | 1985-07-23 | Swisher Gregory M | Polymer blend composition exhibiting impact resistance |
| JPH0774299B2 (en) * | 1986-10-14 | 1995-08-09 | 三菱レイヨン株式会社 | Chlorinated vinyl chloride resin composition |
| US4974493A (en) * | 1988-12-20 | 1990-12-04 | Yeffman Paul L | Shock absorbing buffer and recoil reducer |
| US5079296A (en) * | 1989-07-21 | 1992-01-07 | Polysar Limited | Transparent toughened thermoplastics |
| US5268424A (en) * | 1990-11-29 | 1993-12-07 | The B. F. Goodrich Company | Chlorinated polyvinyl chloride/polycarbonate blend |
| US5900452A (en) | 1996-08-12 | 1999-05-04 | Tactyl Technologies, Inc. | S-EB-S block copolymer/oil aqueous dispersion and its use in forming articles |
| US6593423B1 (en) | 2000-05-03 | 2003-07-15 | Ppg Industries Ohio, Inc. | Adhesion promoting agent and coating compositions for polymeric substrates |
| US20050070663A1 (en) * | 2003-09-29 | 2005-03-31 | Fina Technology, Inc. | Impact modified polystyrene and process for preparing same |
| CN109535618A (en) * | 2018-11-13 | 2019-03-29 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of high stability CPVC tubing and its mixing method |
| CN113829704B (en) * | 2021-09-22 | 2023-03-14 | 杭州久通塑业有限公司 | Impact-resistant modified CPVC power cable sheath pipe |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2011790A1 (en) * | 1968-06-29 | 1970-03-06 | Kanegafuchi Chemical Ind | |
| FR2117185A5 (en) * | 1970-12-02 | 1972-07-21 | Shell Int Research | Biocidal moulding compsn - comprising a pvc resin an elastomeric diene block copolymer and a phosphate plasticiser |
| US3793406A (en) * | 1971-11-21 | 1974-02-19 | Rohm & Haas | Vinyl halide polymer impact modifiers |
| US3801529A (en) * | 1973-02-12 | 1974-04-02 | Shell Oil Co | Block copolymer-polyvinyl chloride compositions |
-
1978
- 1978-03-23 US US05/889,458 patent/US4181644A/en not_active Expired - Lifetime
-
1979
- 1979-02-13 CA CA321,405A patent/CA1111177A/en not_active Expired
- 1979-02-14 NZ NZ189648A patent/NZ189648A/en unknown
- 1979-02-15 AU AU44268/79A patent/AU526198B2/en not_active Ceased
- 1979-02-23 DE DE7979100537T patent/DE2962265D1/en not_active Expired
- 1979-02-23 EP EP79100537A patent/EP0004547B1/en not_active Expired
- 1979-03-23 JP JP3342179A patent/JPS54131653A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU4426879A (en) | 1979-09-27 |
| US4181644A (en) | 1980-01-01 |
| NZ189648A (en) | 1980-12-19 |
| EP0004547A3 (en) | 1979-10-31 |
| AU526198B2 (en) | 1982-12-23 |
| JPS54131653A (en) | 1979-10-12 |
| DE2962265D1 (en) | 1982-04-15 |
| EP0004547B1 (en) | 1982-03-17 |
| EP0004547A2 (en) | 1979-10-17 |
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