CA1229188A - Thermoplastic moulding composition - Google Patents
Thermoplastic moulding compositionInfo
- Publication number
- CA1229188A CA1229188A CA000453438A CA453438A CA1229188A CA 1229188 A CA1229188 A CA 1229188A CA 000453438 A CA000453438 A CA 000453438A CA 453438 A CA453438 A CA 453438A CA 1229188 A CA1229188 A CA 1229188A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Abstract
A B S T R A C T
THERMOPLASTIC MOULDING COMPOSITION
A thermoplastic moulding composition comprising a selecti-vely hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks and at least one wholly or partly hydrogenated conjugated diene polymer mid block, a vinyl aromatic-.alpha.,.beta.-unsaturated cyclic anhydride copolymer, a thermo-plastic polyester and a hydrogenated diblock copolymer. Said composition exhibits an improved balance of cold impact strength and stiffness.
THERMOPLASTIC MOULDING COMPOSITION
A thermoplastic moulding composition comprising a selecti-vely hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks and at least one wholly or partly hydrogenated conjugated diene polymer mid block, a vinyl aromatic-.alpha.,.beta.-unsaturated cyclic anhydride copolymer, a thermo-plastic polyester and a hydrogenated diblock copolymer. Said composition exhibits an improved balance of cold impact strength and stiffness.
Description
l~PIASTIC ~ULDING POSITION
m e present invention relates to a ther~plastic mounding composition.
Vinyl aromatic resins, such as polystyrene or high impact polystyrene, have been found to be useful in thermoplastic mculdin~ compositions. However, such vinyl aromatic resins have poor heat distortion and impact resistance. One approach to improve these property deficiencies involves copolymerizing the vinyl aromatic monomer with an unsaturated cyclic android to form copolymers such as poly(styrene-maleic android). Although such copolymers have improved heat resist-ante, the over-all balance of properties is still inadequate.
In order to further improve the properties of such vinyl aromatic copolymers, various other polymers, such as nitrite rubber, radial styrene-diene block copolymers optionally 15 together with a polyphenylene ether resin, and hydrogenated styrene-diene block copolymers optionally together with a polyphenylene ether resin have been blended with the copolymer.
Such polymer blend compositions are still not fully satisfac-tory.
Further, blends of styrene-maleic android copolymers, hydrogenated styrene-diene-styrene copolymers and thermoplastic polyesters have been disclosed, showing good properties especial-lye when blended with oils. However, this oil can haze into the surface of painted parts made from the material.
The present invention provides a thermoplastic mounding composition having an improved balance of properties, such compositic~ cc~prising:
m e present invention relates to a ther~plastic mounding composition.
Vinyl aromatic resins, such as polystyrene or high impact polystyrene, have been found to be useful in thermoplastic mculdin~ compositions. However, such vinyl aromatic resins have poor heat distortion and impact resistance. One approach to improve these property deficiencies involves copolymerizing the vinyl aromatic monomer with an unsaturated cyclic android to form copolymers such as poly(styrene-maleic android). Although such copolymers have improved heat resist-ante, the over-all balance of properties is still inadequate.
In order to further improve the properties of such vinyl aromatic copolymers, various other polymers, such as nitrite rubber, radial styrene-diene block copolymers optionally 15 together with a polyphenylene ether resin, and hydrogenated styrene-diene block copolymers optionally together with a polyphenylene ether resin have been blended with the copolymer.
Such polymer blend compositions are still not fully satisfac-tory.
Further, blends of styrene-maleic android copolymers, hydrogenated styrene-diene-styrene copolymers and thermoplastic polyesters have been disclosed, showing good properties especial-lye when blended with oils. However, this oil can haze into the surface of painted parts made from the material.
The present invention provides a thermoplastic mounding composition having an improved balance of properties, such compositic~ cc~prising:
- 2 -.
.
(a) 10 - 85 parts by weight of a selectively hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks A and at least one wholly or partly hydrogenated conjugated dine polymer mid block B, said block copolymer, wherein at least 80% of the aliphatic double bonds in block B and no more than 25~ of toe aromatic double bonds in block have been hydrogenated, comprising 8-65 percent by weight of said block A;
(by 10 - 80 parts by weight of a ccpolymer comprising an I unsaturated cyclic android and an aromatic d of the formula - OR - CUR
where m Al and R are selected from the group consisting of Alex or alkenyl groups of frock 1 to 6 carbon atoms and hydra-gent R3 and R are selected from the group consisting of lo sheller, brook, hydrogen and alkyd of frock 1 by 6 carbon atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyd or aLkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydroc3rbyl groups to form a naphthyl group;
(c) 10 - 80 parts by weight of a thermoplastic polyester having a molecular weight in excess of 20,000, a melting point above 12~ C, and which polyester is selected from the group consisting of a polymer of pivalolactone or caprolactone, and a condensation product of a dicarboxylic acid and a glyool; and I 8)~3 (d) 1 - 50 parts by weight of a diabolic copolymer comprising a m~noalkenylarene or hydrogenated noalkenylarene black and a hydrogenated conjugated dine or an alpha olefin block.
The compositions according to the invasion ye readily process able into parts, possess good low temperature (-30 C) properties, are directly paintable with c~nn3rcial paints, have low distortion during to pa my bake cycle usually applied in the art ~120 C, 30 m m.), have excellent gloss, which makes 0 them suitable for exterior automotive applications, and exhibit an improved impact/stiffness balance even without thy incorpo-ration of oil The component tax block copolymers may be linear, radial or branched so long as the copolymer has at least two polymer end blocks A and at least one polymer mid block B. Linear polymers may be prepared by sequential introduction of the desired m~nomPxs into the reaction vessel comprising initiators as lithium~alkyls or dilithiostiIbene, or by coupling a two segnc~lt block copolymer with a difunctional coupling agent.
ranched structures, on the other hand, my be obtained by the use of suitable coupling agents having a functionality with respect to the precursor polymers of three or more. Coupling may be effected with multi functional coupling agents such as dihaloalkanes or -Aquinas and divinyIben2ene, as well as con-lain polo comçcunds such as silicon halides, selections wresters of mandrake alcohols and carboxylic acids. The invent-ion applies especially to the use of selectively hydrogenated polymers having the configuration before hydrogenation of the following typical species:
polystyrene-polybutadiene-polystyrenetSBS) polystyrene-polyisoprene-polystyrene (SKIS) poly(alpha-methylstyrene)-polybutadiene-poly(alphaa-methyl-styrenes and poly(alpha-methylstyrene)-polyisoprene-poly(alpha--methyl sty-none).
It will be understood that both blocks A and B may coauthor a hom~polymer or random copolymer block as long as the monoalkenylarenes predominate in the A blocks and the dines predominate m the B blocks. me term "monoalkenylarene" will be taken to include styrenes and its analogs and homology including alpha-methylstyrene and ring-substituted styrenes.
The preferred mono-aIkenylarenes are styrenes and alpha-methyl-styrQ~nel and styrenes is particularly preferred. me blocks B
may comprise hcmopolymers of butadiene or isoprene and cop-lo lymers of one or both of these two Dennis When the moncmeremployed is butadiene, it is preferred that between 35 and 55 mow percent of the condensed butadiene units in the butadiene polymer block have 1,2 configuration. Thus, when such a block is hydrogenated, the resulting product is or resembles a regular copolymer block of ethylene and buttonhole. If the conjugated dine employed is isoprene, the resulting hydrogen-axed product is or resembles a regular copolymer block of ethylene and propylene.
Hydrogenation of the block copolymers is preferably effected by use of a catalyst comprising the reaction products of an aluminum alkyd compound with nickel or cobalt kooks-fates or alkoxides under such conditions as to hydrogenate at least 80% of the aliphatic double bonds in block B while hydrogenating no more thin 25% of the aromatic double bonds in the A blocks. Preferred block copolymers are those where at least 99% of the aliphatic double bonds in block B and less than 5% of the aromatic double bonds in the A blocks have been hydrogenated.
The average molecular weights of the individual blocks may vary within certain limits. In most instances, the moo-aLkenylarene blocks will have number average molecular weights of S,000-125,000, preferably 7,000-60,000, while the conjugated dine blocks will have average molecular weights of 10,000-300,000, preferably 30,000-150,000. m e total average molecular weight of the block copolymer is 25,000 - 250,000, preferably 35,000 - Tao. These molecular weights are determined by trivium oount~g methods or oC~otic pressure measurements As indicated above the amount of the manoc~lkenylarene blocks in the block ccpolymer is between 8 and 55 percent by wright. Preferably this amount is between 10 and 35 percent by weight of the block copolymer.
While the average molecular weight of the individual blocs is not critical, at least within the above-specified limits, it it useful to select the type and total molecular weight of the block copolymer in order to obtain satisfactory mowing under the chosen blending conditions. Best results cure obtained when the viscosity of the component (a) block cape-lamer and the thermopk~stic resins are substantially tile same at the temperature used for blend m g and process m g. In Skye instances, match m g of the viscosity of the cc~ponent (a) block ccpolymEr portion and the resin portions are best achieved by us m g two or more block copolymers or resins. For example, a blend of two block copolymers having different molecular weights or a blend of a hydrogenated SUBS and a hydrogenated SKIS polymer may be employed.
The ccmpo~ent (b) copolymers are well known in the art.
They comprise an aromatic ccnpound which is represented by the formula:
Curl - CRY
R ~R4 wherein R1 and R2 are selected from the group consistmg of alkyd or aLkenyl groups of from 1 to 6 carbon atoms and ho-drogen; R3 and R4 are selected from the group consisting of sheller, broom/ hydrogen and alkyd of from 1 to 6 carton atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyd or aLkenyl groups of from 1 to 6 carton arcs or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group. Styrenes is the preferred aromatic compound. m eye component by copolymers further comprise an unsaturated cyclic android like malefic android, Satyr-conic android, itaconic android, and aconitic android.
Thy preferred unsaturated cyclic android is Alec android.
These component (b) ccpolymers may comprise 40 to 1 mole percent of the unsaturated cyclic android and from 60 to 99 mole percent of the aromatic compound. The preferred polymers will contain 25-5 mole percent of the unstriated cyclic android old 75-95 mole percent of the aromatic come pound. The preparation of these copolymers is known in the art.
A particularly preferred copolymer is Ayers Dylark 332 which is a styrene-maleic android copolymer containing about 8 mole percent Alec android, the balance being styrenes m e component (c) polyesters employed in the present invention haze a generally crystalline structure. As already mentioned above, they are either a polymer of pivalolactone or caprolactone or a condensation product of a dicarboxylic acid and a glycol.
Among the dicarboxylic acids suitable for preparing polyesters useful in the present invention are oxalic acid, Masonic acid, succinic acid, glutaric acid, adipic acid, sub Eric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p,p'-dicarboxydiphenylsulphone, p-carboxyphe-noxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphe-noxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphen-., oxyhexanoic acid, p,p'-dicarbcxydiphenylmethane, p,p'-dicar-boxydiphenylpropane, p,p'-dicarboxydiphenyloct~ne, alkali-4-~-carbcxyethoxy3benzoic acid, 2,6-naphthalene-dicarboxylic acid and 2,7-napthale~edicarboxylic acid. Mixtures of dicer-bcxylic acids can also be employed. Terephthalic acid ispar~icularly preferred.
Among the glycols suitable for prep King polyesters useful m the present invention are straight chain aquiline glycols of 2 to 12 carbon atoms such as ethylene glycol, 1,3-propylene 10 glycol, 1,6-hexylene glycol, ltlO-decamethylene glycol, 1,12-do-decamethylene glycol and aromatic glycols as pyrocatechol, resorcinol, hydroquinone, or alkyl-substituted derivatives of these compounds. Another suitable glycol is 1,4-cyclohexane dim ethanol. Particularly preferred glycols are the straight lo chain alkaline glycols having 2 to 4 carbon atoms.
Preferred condensation products ye polyethylene turf-thalate), polypropylene terephthalate), and poly(butylene terephthalate). The most preferred polyester is poly(b~ltylene terephthalate). Poly(butylene terephthalate), a crystalline copolymer, may be formed by the polycondensation of byway-tanediol and terephthalic acid, and has the generalized formula:
I
where n varies from 70 to 140. The molecular weight of the Foly(butyLene terephthalate) typically varies from 20,000 to 25,000.
,, .
Another useful polyester is a polymer of pivalolactone.
Preferably this polymer is a pivalolactone homopolymer. Also included, however, are the copolymers of pivalolactone with not more than 50 mole percent of other beta-propiolactones, such as betaproplolactone, alpha,alpha-diethyl-beta-propiolactone and alpha-methyl-alpha-ethyl-beta-propiolactone. The term eta pro piolactones" refers to beta-propiolactone ~Z-oxetanone~ and to derivatives thereof which carry no substitutes at the beta-car-bun atoms of the lactose ring. Preferred beta-propiolactones 0 are those containing a tertiary or qua ternary carbon atcn in the alpha position relative to the carbonyl group. Especially preferred are the alpha,alpha-dialkyl-beta-propiolactones wherein each of the alkyd groups independently has from one to four carbon atoms. Examples of useful mongers are:
, .
alpha-ethyl-alpha-methyl-beta-propiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactone, alpha-ethyl-alpha-n-butyl-beta-propiolactone, alpha-chloromethyl-a.lpha-methyl-beta-propiolactonno, alpha,alpha-bis(chloromethyl)-beta-propiolactone, and alp~la,alpha-dime~hyl-beta-propiolactone (pivalolactone).
Another useful polyester is a polymer of caprolactone.
Typical poly(-caprolactones) are substantially Lear polymers in which the repeating unit is , okay r C~2 C~2 C~2 C~2 1 These polymers have similar properties to the polypiva-lolactones.
Diabolic copolymers according to the present invention are referred to as A-B type in which A represents a block of monoalhenylarenes or hydrogenated products thereof and B
represents a block of alpha olefins or hydrogenated conjugated dines. me average molecular weight of block A is between 5,000 and 75,000 and preferably between 9,000 and 60,000, and that of block B between 10,000 and 1,000,000 and preferably between 15,000 and 200,000.
m e conjugated dines which may be employed in forming the diabolic ccpolymers to be later hydrogenated mclude especially butadiene and isoprene as well as mixtures thereof. If diabolic copolymers are formed with alpha olefins, the preferred species include ethene, propane, butane, and mixtures thereon. The preferred monoalkenylarene is styrenes lo me diabolic copolymers comprising dine blocks are hydra-jointed to reduce their olefinic unsaturation by at least 50 and preferably at least 80~ of the original olefinic double bonds, Hydrogenation is preferably carried out in solution utilizing either homogeneous or heterogeneous catalysts, such as cobalt or nickel salts or alkoxides reduced with aluminum alkyd cc~pounds. Preferably nickel acetate, nickel octet, or nickel acetyl-acetonate reduced with aluminiumaIkyl pounds such as alumLniumtriethyl or aluminiumtriisobutyl are employed.
the polymer blends of the present invention may be come pounded further with other polymers, oils, fillers, reinforcing materials, anti-cxidants, stabilizers, fire retardants, anti-blocking agents and other rubber or plastic cGmpcunding inure-dints without departing from the scope of the present invent-ion.
Reinforcing materials include glass fires, asbestos, boron fires, carbon and graphite fires, whiskers, quartz, and silica fires, ceramic fires, metal fires, natural organic fires, and synthetic organic fires. Especially preferred are reinforced polymer blends of the instant invent-ion containing 2 to 80 percent by weight of a reinforcing material eased on the total weight of the resulting reinforced blend.
The proportions of the polymers are presented below in parts by weight:
Preferred Selectively hydrogenated 10 to 85 30 to 70 block copolymer Vinyl arctic copolymer 10 to 80 15 to 40 Thermoplastic pulsator to 8015 to 40 Hydrogenated diabolic 1 to 50 5 to 20 CQpC lamer The blending of the varicNs polymer cc~ponents may be done in any wanner that produces a blend which will not delaminate lo on processing. For example, the various polymers may be disk solved in a solvent cc on for all and coagulated by ac~Dixing in a solvent in which none of the polymers ye soluble. A
particle lye useful procedure is to intimately mix the polymers m the form of granules and/or pc~der in a high shear mixer.
Intimate mixing is typically achieved by employing high shear extrusion compounding machines such as twin screw compounding extrudes and thermoplastic extrudes having at least 20:1 length/diameter ratio and a compression ratio of 3 or 4:1.
The mixing or processing temperature is selected in accordance with the pa titular polymers to be blended. For example, when melt blending the polymers instead of solution blending, it will be necessary to select a processing tempo-nature above the melting point of the highest melting point polymer. In addition, the processing temperature may also be chosen so as to permit the isoviscous mixing of the polymers.
; Typically, the mixing or processing temperature is between 200 C and 350 C. For blends containing poly~butylene turf-thalate~ the mixing or processing temperature is preferably between 240 C and 300 C~
,, The polymer blends of the present invention can be employ-Ed in any use typically performed by engineering thermoplastics, such as metal replacement and those areas where high performance is necessary. A particularly useful end use area is for exterior decorated automotive applications.
The present invention is illustrated by the following Example The physical test methods used in evaluation of the blends appeasing in the Table are as follows:
-30 C Cold Impact Strength Gardner Impact Test Stiff-news -- Tunis Olsen Stiffness Test, Arm D-747.
Example Various polymer blends are prepared by first dry blerlding the various component particles, and then extruding the result-in mixture in a Werner-Pflederer extrude at a temperature above 240 C.
As component (a) three different selectively hydrogenated polystyrene-polybutadiene-polystyrene block copolymers are employed, wherein more than 99% of the original olefinic double bonds have been hydrogenated. me molecular weight of these block copolymers, which have been numbered l, 2 and 3 in Table 1, is 100,000, 76,000 and 144,000 respectively and their styrenes content is 30, 30 an wow respectively. Component IBM
is Dylark 332.
me thermoplastic polyester is poly~butylene terepht~ late (PUT), having a molecular weigh of 35,000 and a melting point of 225C.
The diabolic copolymer is a polystyrene-polyisoprene block copolymer wherein more than 99% of the original olefinic double Jo bonds has been hydrogenated; the molecule weight is 142,000 and the styrenes content is 37~ w. Further data and results are presented in Table l.
The compositions according to the present invention exhibit a high impact strength together with a high stiffness without the use of oil. muse blends also skew significant improvements in surface scuff and mar resistance and do not show signs of hazing as in the oiled blends.
_ 12 -Us I o o Lo Lo I t--Jo CO
It r I I In I ED
I
or I I co co o I us o .
o I I O O I I I 0 .
ox -I
I U
P o I m o C) I
.
(a) 10 - 85 parts by weight of a selectively hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks A and at least one wholly or partly hydrogenated conjugated dine polymer mid block B, said block copolymer, wherein at least 80% of the aliphatic double bonds in block B and no more than 25~ of toe aromatic double bonds in block have been hydrogenated, comprising 8-65 percent by weight of said block A;
(by 10 - 80 parts by weight of a ccpolymer comprising an I unsaturated cyclic android and an aromatic d of the formula - OR - CUR
where m Al and R are selected from the group consisting of Alex or alkenyl groups of frock 1 to 6 carbon atoms and hydra-gent R3 and R are selected from the group consisting of lo sheller, brook, hydrogen and alkyd of frock 1 by 6 carbon atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyd or aLkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydroc3rbyl groups to form a naphthyl group;
(c) 10 - 80 parts by weight of a thermoplastic polyester having a molecular weight in excess of 20,000, a melting point above 12~ C, and which polyester is selected from the group consisting of a polymer of pivalolactone or caprolactone, and a condensation product of a dicarboxylic acid and a glyool; and I 8)~3 (d) 1 - 50 parts by weight of a diabolic copolymer comprising a m~noalkenylarene or hydrogenated noalkenylarene black and a hydrogenated conjugated dine or an alpha olefin block.
The compositions according to the invasion ye readily process able into parts, possess good low temperature (-30 C) properties, are directly paintable with c~nn3rcial paints, have low distortion during to pa my bake cycle usually applied in the art ~120 C, 30 m m.), have excellent gloss, which makes 0 them suitable for exterior automotive applications, and exhibit an improved impact/stiffness balance even without thy incorpo-ration of oil The component tax block copolymers may be linear, radial or branched so long as the copolymer has at least two polymer end blocks A and at least one polymer mid block B. Linear polymers may be prepared by sequential introduction of the desired m~nomPxs into the reaction vessel comprising initiators as lithium~alkyls or dilithiostiIbene, or by coupling a two segnc~lt block copolymer with a difunctional coupling agent.
ranched structures, on the other hand, my be obtained by the use of suitable coupling agents having a functionality with respect to the precursor polymers of three or more. Coupling may be effected with multi functional coupling agents such as dihaloalkanes or -Aquinas and divinyIben2ene, as well as con-lain polo comçcunds such as silicon halides, selections wresters of mandrake alcohols and carboxylic acids. The invent-ion applies especially to the use of selectively hydrogenated polymers having the configuration before hydrogenation of the following typical species:
polystyrene-polybutadiene-polystyrenetSBS) polystyrene-polyisoprene-polystyrene (SKIS) poly(alpha-methylstyrene)-polybutadiene-poly(alphaa-methyl-styrenes and poly(alpha-methylstyrene)-polyisoprene-poly(alpha--methyl sty-none).
It will be understood that both blocks A and B may coauthor a hom~polymer or random copolymer block as long as the monoalkenylarenes predominate in the A blocks and the dines predominate m the B blocks. me term "monoalkenylarene" will be taken to include styrenes and its analogs and homology including alpha-methylstyrene and ring-substituted styrenes.
The preferred mono-aIkenylarenes are styrenes and alpha-methyl-styrQ~nel and styrenes is particularly preferred. me blocks B
may comprise hcmopolymers of butadiene or isoprene and cop-lo lymers of one or both of these two Dennis When the moncmeremployed is butadiene, it is preferred that between 35 and 55 mow percent of the condensed butadiene units in the butadiene polymer block have 1,2 configuration. Thus, when such a block is hydrogenated, the resulting product is or resembles a regular copolymer block of ethylene and buttonhole. If the conjugated dine employed is isoprene, the resulting hydrogen-axed product is or resembles a regular copolymer block of ethylene and propylene.
Hydrogenation of the block copolymers is preferably effected by use of a catalyst comprising the reaction products of an aluminum alkyd compound with nickel or cobalt kooks-fates or alkoxides under such conditions as to hydrogenate at least 80% of the aliphatic double bonds in block B while hydrogenating no more thin 25% of the aromatic double bonds in the A blocks. Preferred block copolymers are those where at least 99% of the aliphatic double bonds in block B and less than 5% of the aromatic double bonds in the A blocks have been hydrogenated.
The average molecular weights of the individual blocks may vary within certain limits. In most instances, the moo-aLkenylarene blocks will have number average molecular weights of S,000-125,000, preferably 7,000-60,000, while the conjugated dine blocks will have average molecular weights of 10,000-300,000, preferably 30,000-150,000. m e total average molecular weight of the block copolymer is 25,000 - 250,000, preferably 35,000 - Tao. These molecular weights are determined by trivium oount~g methods or oC~otic pressure measurements As indicated above the amount of the manoc~lkenylarene blocks in the block ccpolymer is between 8 and 55 percent by wright. Preferably this amount is between 10 and 35 percent by weight of the block copolymer.
While the average molecular weight of the individual blocs is not critical, at least within the above-specified limits, it it useful to select the type and total molecular weight of the block copolymer in order to obtain satisfactory mowing under the chosen blending conditions. Best results cure obtained when the viscosity of the component (a) block cape-lamer and the thermopk~stic resins are substantially tile same at the temperature used for blend m g and process m g. In Skye instances, match m g of the viscosity of the cc~ponent (a) block ccpolymEr portion and the resin portions are best achieved by us m g two or more block copolymers or resins. For example, a blend of two block copolymers having different molecular weights or a blend of a hydrogenated SUBS and a hydrogenated SKIS polymer may be employed.
The ccmpo~ent (b) copolymers are well known in the art.
They comprise an aromatic ccnpound which is represented by the formula:
Curl - CRY
R ~R4 wherein R1 and R2 are selected from the group consistmg of alkyd or aLkenyl groups of from 1 to 6 carbon atoms and ho-drogen; R3 and R4 are selected from the group consisting of sheller, broom/ hydrogen and alkyd of from 1 to 6 carton atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyd or aLkenyl groups of from 1 to 6 carton arcs or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group. Styrenes is the preferred aromatic compound. m eye component by copolymers further comprise an unsaturated cyclic android like malefic android, Satyr-conic android, itaconic android, and aconitic android.
Thy preferred unsaturated cyclic android is Alec android.
These component (b) ccpolymers may comprise 40 to 1 mole percent of the unsaturated cyclic android and from 60 to 99 mole percent of the aromatic compound. The preferred polymers will contain 25-5 mole percent of the unstriated cyclic android old 75-95 mole percent of the aromatic come pound. The preparation of these copolymers is known in the art.
A particularly preferred copolymer is Ayers Dylark 332 which is a styrene-maleic android copolymer containing about 8 mole percent Alec android, the balance being styrenes m e component (c) polyesters employed in the present invention haze a generally crystalline structure. As already mentioned above, they are either a polymer of pivalolactone or caprolactone or a condensation product of a dicarboxylic acid and a glycol.
Among the dicarboxylic acids suitable for preparing polyesters useful in the present invention are oxalic acid, Masonic acid, succinic acid, glutaric acid, adipic acid, sub Eric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p,p'-dicarboxydiphenylsulphone, p-carboxyphe-noxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphe-noxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphen-., oxyhexanoic acid, p,p'-dicarbcxydiphenylmethane, p,p'-dicar-boxydiphenylpropane, p,p'-dicarboxydiphenyloct~ne, alkali-4-~-carbcxyethoxy3benzoic acid, 2,6-naphthalene-dicarboxylic acid and 2,7-napthale~edicarboxylic acid. Mixtures of dicer-bcxylic acids can also be employed. Terephthalic acid ispar~icularly preferred.
Among the glycols suitable for prep King polyesters useful m the present invention are straight chain aquiline glycols of 2 to 12 carbon atoms such as ethylene glycol, 1,3-propylene 10 glycol, 1,6-hexylene glycol, ltlO-decamethylene glycol, 1,12-do-decamethylene glycol and aromatic glycols as pyrocatechol, resorcinol, hydroquinone, or alkyl-substituted derivatives of these compounds. Another suitable glycol is 1,4-cyclohexane dim ethanol. Particularly preferred glycols are the straight lo chain alkaline glycols having 2 to 4 carbon atoms.
Preferred condensation products ye polyethylene turf-thalate), polypropylene terephthalate), and poly(butylene terephthalate). The most preferred polyester is poly(b~ltylene terephthalate). Poly(butylene terephthalate), a crystalline copolymer, may be formed by the polycondensation of byway-tanediol and terephthalic acid, and has the generalized formula:
I
where n varies from 70 to 140. The molecular weight of the Foly(butyLene terephthalate) typically varies from 20,000 to 25,000.
,, .
Another useful polyester is a polymer of pivalolactone.
Preferably this polymer is a pivalolactone homopolymer. Also included, however, are the copolymers of pivalolactone with not more than 50 mole percent of other beta-propiolactones, such as betaproplolactone, alpha,alpha-diethyl-beta-propiolactone and alpha-methyl-alpha-ethyl-beta-propiolactone. The term eta pro piolactones" refers to beta-propiolactone ~Z-oxetanone~ and to derivatives thereof which carry no substitutes at the beta-car-bun atoms of the lactose ring. Preferred beta-propiolactones 0 are those containing a tertiary or qua ternary carbon atcn in the alpha position relative to the carbonyl group. Especially preferred are the alpha,alpha-dialkyl-beta-propiolactones wherein each of the alkyd groups independently has from one to four carbon atoms. Examples of useful mongers are:
, .
alpha-ethyl-alpha-methyl-beta-propiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactone, alpha-ethyl-alpha-n-butyl-beta-propiolactone, alpha-chloromethyl-a.lpha-methyl-beta-propiolactonno, alpha,alpha-bis(chloromethyl)-beta-propiolactone, and alp~la,alpha-dime~hyl-beta-propiolactone (pivalolactone).
Another useful polyester is a polymer of caprolactone.
Typical poly(-caprolactones) are substantially Lear polymers in which the repeating unit is , okay r C~2 C~2 C~2 C~2 1 These polymers have similar properties to the polypiva-lolactones.
Diabolic copolymers according to the present invention are referred to as A-B type in which A represents a block of monoalhenylarenes or hydrogenated products thereof and B
represents a block of alpha olefins or hydrogenated conjugated dines. me average molecular weight of block A is between 5,000 and 75,000 and preferably between 9,000 and 60,000, and that of block B between 10,000 and 1,000,000 and preferably between 15,000 and 200,000.
m e conjugated dines which may be employed in forming the diabolic ccpolymers to be later hydrogenated mclude especially butadiene and isoprene as well as mixtures thereof. If diabolic copolymers are formed with alpha olefins, the preferred species include ethene, propane, butane, and mixtures thereon. The preferred monoalkenylarene is styrenes lo me diabolic copolymers comprising dine blocks are hydra-jointed to reduce their olefinic unsaturation by at least 50 and preferably at least 80~ of the original olefinic double bonds, Hydrogenation is preferably carried out in solution utilizing either homogeneous or heterogeneous catalysts, such as cobalt or nickel salts or alkoxides reduced with aluminum alkyd cc~pounds. Preferably nickel acetate, nickel octet, or nickel acetyl-acetonate reduced with aluminiumaIkyl pounds such as alumLniumtriethyl or aluminiumtriisobutyl are employed.
the polymer blends of the present invention may be come pounded further with other polymers, oils, fillers, reinforcing materials, anti-cxidants, stabilizers, fire retardants, anti-blocking agents and other rubber or plastic cGmpcunding inure-dints without departing from the scope of the present invent-ion.
Reinforcing materials include glass fires, asbestos, boron fires, carbon and graphite fires, whiskers, quartz, and silica fires, ceramic fires, metal fires, natural organic fires, and synthetic organic fires. Especially preferred are reinforced polymer blends of the instant invent-ion containing 2 to 80 percent by weight of a reinforcing material eased on the total weight of the resulting reinforced blend.
The proportions of the polymers are presented below in parts by weight:
Preferred Selectively hydrogenated 10 to 85 30 to 70 block copolymer Vinyl arctic copolymer 10 to 80 15 to 40 Thermoplastic pulsator to 8015 to 40 Hydrogenated diabolic 1 to 50 5 to 20 CQpC lamer The blending of the varicNs polymer cc~ponents may be done in any wanner that produces a blend which will not delaminate lo on processing. For example, the various polymers may be disk solved in a solvent cc on for all and coagulated by ac~Dixing in a solvent in which none of the polymers ye soluble. A
particle lye useful procedure is to intimately mix the polymers m the form of granules and/or pc~der in a high shear mixer.
Intimate mixing is typically achieved by employing high shear extrusion compounding machines such as twin screw compounding extrudes and thermoplastic extrudes having at least 20:1 length/diameter ratio and a compression ratio of 3 or 4:1.
The mixing or processing temperature is selected in accordance with the pa titular polymers to be blended. For example, when melt blending the polymers instead of solution blending, it will be necessary to select a processing tempo-nature above the melting point of the highest melting point polymer. In addition, the processing temperature may also be chosen so as to permit the isoviscous mixing of the polymers.
; Typically, the mixing or processing temperature is between 200 C and 350 C. For blends containing poly~butylene turf-thalate~ the mixing or processing temperature is preferably between 240 C and 300 C~
,, The polymer blends of the present invention can be employ-Ed in any use typically performed by engineering thermoplastics, such as metal replacement and those areas where high performance is necessary. A particularly useful end use area is for exterior decorated automotive applications.
The present invention is illustrated by the following Example The physical test methods used in evaluation of the blends appeasing in the Table are as follows:
-30 C Cold Impact Strength Gardner Impact Test Stiff-news -- Tunis Olsen Stiffness Test, Arm D-747.
Example Various polymer blends are prepared by first dry blerlding the various component particles, and then extruding the result-in mixture in a Werner-Pflederer extrude at a temperature above 240 C.
As component (a) three different selectively hydrogenated polystyrene-polybutadiene-polystyrene block copolymers are employed, wherein more than 99% of the original olefinic double bonds have been hydrogenated. me molecular weight of these block copolymers, which have been numbered l, 2 and 3 in Table 1, is 100,000, 76,000 and 144,000 respectively and their styrenes content is 30, 30 an wow respectively. Component IBM
is Dylark 332.
me thermoplastic polyester is poly~butylene terepht~ late (PUT), having a molecular weigh of 35,000 and a melting point of 225C.
The diabolic copolymer is a polystyrene-polyisoprene block copolymer wherein more than 99% of the original olefinic double Jo bonds has been hydrogenated; the molecule weight is 142,000 and the styrenes content is 37~ w. Further data and results are presented in Table l.
The compositions according to the present invention exhibit a high impact strength together with a high stiffness without the use of oil. muse blends also skew significant improvements in surface scuff and mar resistance and do not show signs of hazing as in the oiled blends.
_ 12 -Us I o o Lo Lo I t--Jo CO
It r I I In I ED
I
or I I co co o I us o .
o I I O O I I I 0 .
ox -I
I U
P o I m o C) I
Claims (5)
1. A thermoplastic moulding composition comprising:
(a) 10 - 85 parts by weight of a selectively hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks A and at least one wholly or partly hydrogenated conjugated diene polymer mid block B, said block copolymer, wherein at least 80% of the aliphatic double bonds in block B and no more than 25% of the aromatic double bonds in block A have been hydrogenated, comprising 8-65 percent by weight of said block A;
(b) 10 - 80 parts by weight of a copolymer comprising an .alpha.,.beta.-unsaturated cyclic anhydride and an aromatic compound of the formula wherein R1 and R2 are selected from the group consisting of alkyl or alkenyl groups of from 1 to 6 carbon atoms and hydro-gen; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen and alkyl of from 1 to 6 carbon atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyl or alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group;
(c) 10 - 80 parts by weight of a thermoplastic polyester having a molecular weight in excess of 20,000, a melting point above 120 °C, and which polyester is selected from the group consisting of a polymer of pivalolactone or caprolactone, and a condensation product of a dicarboxylic acid and a glycol; and (d) 1 - 50 parts by weight of a diblock copolymer comprising a monoalkenylarene or hydrogenated monoalkenylarene block and a hydrogenated conjugated diene or an alpha olefin block.
(a) 10 - 85 parts by weight of a selectively hydrogenated block copolymer comprising at least two monoalkenylarene polymer end blocks A and at least one wholly or partly hydrogenated conjugated diene polymer mid block B, said block copolymer, wherein at least 80% of the aliphatic double bonds in block B and no more than 25% of the aromatic double bonds in block A have been hydrogenated, comprising 8-65 percent by weight of said block A;
(b) 10 - 80 parts by weight of a copolymer comprising an .alpha.,.beta.-unsaturated cyclic anhydride and an aromatic compound of the formula wherein R1 and R2 are selected from the group consisting of alkyl or alkenyl groups of from 1 to 6 carbon atoms and hydro-gen; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen and alkyl of from 1 to 6 carbon atoms;
R5 and R6 are selected from the group consisting of hydrogen and alkyl or alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group;
(c) 10 - 80 parts by weight of a thermoplastic polyester having a molecular weight in excess of 20,000, a melting point above 120 °C, and which polyester is selected from the group consisting of a polymer of pivalolactone or caprolactone, and a condensation product of a dicarboxylic acid and a glycol; and (d) 1 - 50 parts by weight of a diblock copolymer comprising a monoalkenylarene or hydrogenated monoalkenylarene block and a hydrogenated conjugated diene or an alpha olefin block.
2. A thermoplastic moulding composition according to claim 1, characterized in that the selectively hydrogenated block copolymer is a linear ABA block copolymer.
3. A thermoplastic moulding composition according to claim 1, characterized in that the copolymer comprising the .alpha.,.beta.-unsatur-ated cyclic anhydride and the aromatic compound is a styrene-maleic anhydride copolymer.
4. A thermoplastic moulding composition according to claims 1, 2 or 3, characterized in that the thermoplastic polyester is a condensation product of a dicarboxylic acid with a glycol.
5. A thermoplastic moulding composition according to claims 1, 2, or 3 characterized in that the thermoplastic polyester is poly(butylene terephthalate).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US502,407 | 1983-06-08 | ||
| US06/502,407 US4493919A (en) | 1983-06-08 | 1983-06-08 | Polymer blend composition comprising two block polymers a vinyl aromatic copolymer and a polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229188A true CA1229188A (en) | 1987-11-10 |
Family
ID=23997678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000453438A Expired CA1229188A (en) | 1983-06-08 | 1984-05-03 | Thermoplastic moulding composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4493919A (en) |
| EP (1) | EP0128598B1 (en) |
| JP (1) | JPS606744A (en) |
| AU (1) | AU564126B2 (en) |
| CA (1) | CA1229188A (en) |
| DE (1) | DE3463664D1 (en) |
| ES (1) | ES8605012A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491648A (en) * | 1984-05-29 | 1985-01-01 | Shell Oil Company | Polymer blend composition |
| US4601941A (en) * | 1984-09-07 | 1986-07-22 | Shell Oil Company | High heat metal-polymer laminate |
| CA1289686C (en) * | 1985-07-31 | 1991-09-24 | Richard Gelles | Impact resistant polymeric compositions |
| JPS638450A (en) * | 1986-06-27 | 1988-01-14 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| WO1989005837A1 (en) * | 1986-06-27 | 1989-06-29 | Shell Internationale Research Maatschappij B.V. | Thermoplastic elastomer compositions and process for the preparation thereof |
| US5318854A (en) * | 1986-08-26 | 1994-06-07 | General Electric Co. | Polymer mixture based on a polybutylene terephthalate ester and a S-MA copolymer and films made thereof |
| US4769415A (en) * | 1987-06-09 | 1988-09-06 | Dainippon Plastics Co., Ltd. | Resin composition |
| US5082892A (en) * | 1989-03-02 | 1992-01-21 | Idemitsu Petrochemical Company, Ltd. | Novel resin composition and chassis for electronic instruments shaped therefrom |
| US5340875A (en) * | 1991-08-15 | 1994-08-23 | Arco Chemical Technology | Blends of polybutylene terephthalate resins and methacrylic acid-containing styrenic copolymers |
| US5545792A (en) * | 1994-11-21 | 1996-08-13 | Amoco Corporation | Isomerization catalyst and process |
| US8126840B2 (en) * | 2007-10-22 | 2012-02-28 | Noria Corporation | Lubrication program management system and methods |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4243766A (en) * | 1974-06-07 | 1981-01-06 | General Electric Company | Thermoplastic molding compositions of vinyl aromatic compound α,.beta. |
| US4081424A (en) * | 1976-06-07 | 1978-03-28 | Shell Oil Company | Multicomponent polyolefin - block copolymer - polymer blends |
| US4220735A (en) * | 1978-12-18 | 1980-09-02 | General Electric Company | Modified polyester compositions |
| US4267286A (en) * | 1979-07-03 | 1981-05-12 | General Electric Company | Modified polyester compositions |
| US4277575A (en) * | 1979-10-02 | 1981-07-07 | General Electric Company | Impact modifier for thermoplastic compositions |
| US4377647A (en) * | 1981-11-16 | 1983-03-22 | Shell Oil Company | Polymer blend composition |
-
1983
- 1983-06-08 US US06/502,407 patent/US4493919A/en not_active Expired - Lifetime
-
1984
- 1984-05-02 DE DE8484200613T patent/DE3463664D1/en not_active Expired
- 1984-05-02 EP EP84200613A patent/EP0128598B1/en not_active Expired
- 1984-05-03 CA CA000453438A patent/CA1229188A/en not_active Expired
- 1984-06-06 ES ES533158A patent/ES8605012A1/en not_active Expired
- 1984-06-06 JP JP59114731A patent/JPS606744A/en active Granted
- 1984-06-06 AU AU29130/84A patent/AU564126B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES533158A0 (en) | 1986-02-16 |
| US4493919A (en) | 1985-01-15 |
| AU564126B2 (en) | 1987-07-30 |
| DE3463664D1 (en) | 1987-06-19 |
| EP0128598B1 (en) | 1987-05-13 |
| AU2913084A (en) | 1984-12-13 |
| ES8605012A1 (en) | 1986-02-16 |
| JPH0573781B2 (en) | 1993-10-15 |
| EP0128598A1 (en) | 1984-12-19 |
| JPS606744A (en) | 1985-01-14 |
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