CA2103420A1 - Stabilization of low molecular weight polybutylene terephthalate/polyester blends with phosphorus compounds - Google Patents
Stabilization of low molecular weight polybutylene terephthalate/polyester blends with phosphorus compoundsInfo
- Publication number
- CA2103420A1 CA2103420A1 CA002103420A CA2103420A CA2103420A1 CA 2103420 A1 CA2103420 A1 CA 2103420A1 CA 002103420 A CA002103420 A CA 002103420A CA 2103420 A CA2103420 A CA 2103420A CA 2103420 A1 CA2103420 A1 CA 2103420A1
- Authority
- CA
- Canada
- Prior art keywords
- thermoplastic resin
- resin blend
- phosphite
- molecular weight
- component
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
Abstract
ABSTRACT OF THE PRESENT INVENTION
Blends of low molecular weight PBT resin and high molecular weight polyester resin, such as high molecular weight PBT resin, are imparted with excellent melt viscosity stability by the addition of certain phosphorus-containing compounds.
Blends of low molecular weight PBT resin and high molecular weight polyester resin, such as high molecular weight PBT resin, are imparted with excellent melt viscosity stability by the addition of certain phosphorus-containing compounds.
Description
- 2103~2(~
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- l 8CV-S401 STABILIZATION OF LOW MOLECULAR WEIGHT POLYBUTYLENE
~EREPHT~ALATE/POLYESTEX BLENDS WITH PHOSPHORVS COMPOUNDS
The pxesent inven~.ion rela~es to blends of low molecular weight polybutylene terephthalate resins and high molecular weight polyester re3ins having improved : melt viscosity stability.
BACKGRQUND OF THE PRESENT INVENTION
Polyester resins derived from terephthalic aci~
and reactive derivatives thereof, such as dime~hylene terephthalate, and alkane diols, e.g., of from 1 to 10 ~ carbon atoms, e.g., ethylene glycol, and 1,4-butanediol, as well as related diols, such as 1,4-cyclohexane dimethanol, and mixtures of such resins have been known for some time and have become important constituents in ' 15 injection moldable compositions. Workpieces molded from : such polyester compositions, alone, or combined with reinforcments, offer a high degree of surface hardness l and abrasion resistance, high gloss, and lower surface ¦ friction.
Accordingly, polyesters have found significant i commercial applications. Polyesters are effectively used ., as an en~ineering plastic for electrical components, ¦ machines, cars, sporting goods, interior decorative goods and the like. For many of the~e applications it i~
desirable to employ a polyester resin having a relatively . high molecular weight, i.e., having a melt viscosity of above about 600 poise as measured using a Tinium Olsen -~ melt indexer at 250C, 0.042 inch oriflce (ASTM method D-1238); or having an intrinsic vi~c05i'~y of above about ~, 30 0.6 decaliterstgram as measured using a 120-130 mg sample of polyestar in a 3:2 mixture of phenol/tetra-chloroethane and measuring the time of flow with a Ubbelohde capillary viscometer at 25C.
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- l 8CV-S401 STABILIZATION OF LOW MOLECULAR WEIGHT POLYBUTYLENE
~EREPHT~ALATE/POLYESTEX BLENDS WITH PHOSPHORVS COMPOUNDS
The pxesent inven~.ion rela~es to blends of low molecular weight polybutylene terephthalate resins and high molecular weight polyester re3ins having improved : melt viscosity stability.
BACKGRQUND OF THE PRESENT INVENTION
Polyester resins derived from terephthalic aci~
and reactive derivatives thereof, such as dime~hylene terephthalate, and alkane diols, e.g., of from 1 to 10 ~ carbon atoms, e.g., ethylene glycol, and 1,4-butanediol, as well as related diols, such as 1,4-cyclohexane dimethanol, and mixtures of such resins have been known for some time and have become important constituents in ' 15 injection moldable compositions. Workpieces molded from : such polyester compositions, alone, or combined with reinforcments, offer a high degree of surface hardness l and abrasion resistance, high gloss, and lower surface ¦ friction.
Accordingly, polyesters have found significant i commercial applications. Polyesters are effectively used ., as an en~ineering plastic for electrical components, ¦ machines, cars, sporting goods, interior decorative goods and the like. For many of the~e applications it i~
desirable to employ a polyester resin having a relatively . high molecular weight, i.e., having a melt viscosity of above about 600 poise as measured using a Tinium Olsen -~ melt indexer at 250C, 0.042 inch oriflce (ASTM method D-1238); or having an intrinsic vi~c05i'~y of above about ~, 30 0.6 decaliterstgram as measured using a 120-130 mg sample of polyestar in a 3:2 mixture of phenol/tetra-chloroethane and measuring the time of flow with a Ubbelohde capillary viscometer at 25C.
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2~034~
. 2 ~CV-5401 However, a problem which many pla tics operators have exprienced with high molecular weight polyesters is the di~ficulty in processiny the resins.
In response thereto, a relatively low molecular weight PBT, less than about 600 poise, as measured using a Tinius Olsen melt ind~xer at 250C', 0.042 inch orifice (ASTM method D-1238~ has been added to the high molecular weight polyester to provide improved flow blends which ~ still retain the exc~llent propertie~ of the high - 10 moleculax weight polyester. Howevex, it has been found that while the blends of high molecular weight polyester and low molecular weight PBT initially exhibit a decrease in melt viscosity, the melt viscosity builds over time.
; See Figure 1. Such a build up of viscosity of the blends limits the use of low molecular weight PBT in commercial `; applications. It would therefore represent a notable advance in the state of the art if a more stable high . flow blend of a high molecular weight polyester and low - molecular weiyht PBT could be found.
Jacquiss et al., United States Patent No.
4,532,290, teach stabilizing polycarbonate-polyester compositions against undesirable changes in melting point by adding monosodium phosphate and/or monopotassium phosphate to the compositions. Hepp, United States Patent No. 4,687,802, discloses that the arc track rate of PBT resins can be improved by the addition of a metal ~, salt to the PBT resin.
However, none of the prior art teachings suggests a method of preparing a stable high flow blend of a hiyh molecular weight polyester and a low molecular weight PBT. Surprisingly, the present inventor has now found that if certain phosphorus-oontaining compounds are added to the blends of high molecular weight polyester ;~ and low molecular weight P~T, there is achieved a high flow blend having excellent melt stability.
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--2~03~20 ~3CV-5401 BRIEF DESCRIPTION OF T~E DRAWNINGS
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FIGURE 1 depicts in graphic form a comparison of a time sweep of the melt viscosity of an unstabilized blend of a high molecular weight PBT (1100 poise) resin and a low molecular weight (300 poise) PBT resin (Line A) against a time sweep of a high molecular we~gh~ PBT resin : (Line B).
FIGURE 2 depicts in graphic form a comparison of time sweeps of blends of high molecular weight PBT
. 10 and low molecular weight PBT with various additives from A the data set forth in Table 1 hereinbelow.
SUMMARY OF THE PRESENT INVENTION
According to the present invention there is disclosed~a ~hermoplastic resin blend comprising~ ~a) a relatively low molecular weight polybutylene terephthalate resin; (b) a relatively high molecular weight polyester resin; and (c) an effective melt viscosi~y s~abilizing amount of (i) an acidic pho~phate salt, til) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl qroup, (iii) a Group IB or IIB metal phosphate salt (iv) a phosphorous oxo aci~ or . (v) a mixture of any of the foregoing.
:~, Also according to the present invention there is pro~ided a process for stabilizing the melt viscosity of a thermoplastic resin blend comprising a relatively low molecular weigh~ PBT resin and a relatively high molecular weight polyester resin comprising adding to the blend an ~ffective amount of a (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl group, (iii) a Group IB or IIB metal phosphate salt (iv) a phosphorous oxo acid or (v) a mixtuxe of any of the foregoing.
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21~3~20 4 ~CV-5401 ' DETAILED DESCRIPTION OF THE PFIESE?IT INVENTION
The low molecular weight polybutylene terephthalate (PB~) useful in the practice of the present invention is a PBT resin having a melt viscosity of less than 600 poise, more prefexably less than about 450 -. poise, and most preferably less than about 300 poise.
~`~ The high molecular weight polyester resins useful in the practice of the present invention are polyester resins having a melt viscosity above about 600 poise, more preferably above about 900 poise, and mos~
preferably above about 1100 poise~ Preferred as the high molecular weight polyester resins are high molecular weight polybutylene terephthalate, polyethylene :, terephthalate and polycyclohexane dimethylene : 15 terephthalate.
The low molecular weight polybutylene tereph halate resin employed in the present invention is typically one obtained by polymerizing a glycol component at least 70 mol %, preferably at least 80 mol %, of which comprises a tetramethylene glycol; and an acid component at least 70 mol %, preferably at least 80 mol %, of which comprises terephthalic acid/ and polyester-forming deriva~ives thereof. Particularly us~ful is poly(l,4-butylene terephthalate).
Prefer~bly) the glycol does not contain more than 30 mol %, more preferably not more than 20 mol %, of another glycol, such as ethylene glycol, trimethylene glycol, 2-methyl-1,3-propane glycol, hexamethylene glycol, decam~thylene glycol, cyclohexane dimethanol, or neopentylene glycol. Examples of o~her copolycondensable polyols include 1,3-propylene glycol, pentaerythritol, 1,6-hexanediol, polyethylene glycol and polytetra-methylene glycol.
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Preferably the acid component contains no~ more than 30 mol %, more preferably not nnore than 20 mol %, of : another acid such as isophthalic acid, 2,6-, . .
..naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic .5 acid, 1,5-naphthalenedicarboxylic acid, 4,4'-diphenyl-dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, ~:p-hydroxy benzoic acid, sebacic acid, adipic acid and ,'T,,polyester-forming derivatives thereof. Examples of other ,~copolycondensable polycarboxylic acidis include azelaic 5"10 acid, dodecane dicarboxylic acid, trimellitic acid, trimesic acid and hexahydroterephthalic acid.
~;.The low molecular weight PBT resin~ can be ~.prepared according to methods known to those of ordinary !''skill in the art, or they may he obtained commercially.
15 Low molecular weight PBT is VALOX~ 195 having a melt viscosity of about 300 poise from General Electric `~ Company.
The high molecular weight polyester resins are those which are prepared in similar ma~ner to the low 20 molecular weight PBT, i.e., by polymerizing a glycol ,component and an acid componen~. Typically they are .~derived from an aliphatic or cycloalipha~ic ~iol, or ,mixture~ thereof, containing from 2 to about 10 carbon -atoms and at lea~t one aromatic dicarboxylic acid.
25 Preferred polyes~ers ar~ derived from an alipha~ic diol :~and an aromatic dicarboxylic acid and have repeating -~units of the ollo~ing general formula :
,- O
,, 1~
; 30 -t-CH2 ~ 0 - C ~ C
-;~ wherein n is an integer of fro~ 2 to 6. The most ~i preferred polyesters are poly(ethylene terephthalate), poly(l~4-butylene terephthalate) and mixtures thereof.
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~3~20 6 8~V-5401 Al~o contemplated for Us~! herein as the high molecular weight polyesters, are the above polyesters with minor amounts, e.g., from 0.5 to about 5 percent by weight, of units derived from aliphatic acids and/or aliphatic polyols to form copolyesters. The aliphatic polyols include glycols, such as poly(ethylene glycol).
All such polyesters can be made following the teachings of, for example, United States Pat~nt Nos. 2,465,319 and 3,047,539.
Also useful as the high molecular weight polyesters are those derived from a cycloaliphatic diol and an aromatic dicarboxylic acid and which are prepared, for example, by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-cyclohexanedimethanol with an aromatic dicarboxylic acid so as to produce a polye ter having recurring units of the following formula:
O O
--O -- CH2 0 CH2--O-- C ~ C
., ~0 wherein the cyclohexane ring is selected Prom the Ci5-and trans- iso~rs thereof and R represents an aryl radical containing from 6 to about 20 carbon atoms and which is the decarboxylated re~idue derived from an aromatic dicarboxylic acid.
. Examples of arom~tic dicarboxylic acids I represented by ~he decarboxylated residue R are isophthalic or terephthalic acid, 1,2-di-~p-. carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl etherS etc., and mixtures of the~e. All o these acids contain at l ast on~ aromatic nucleu~. Acids containing fused rings can also be present, such as in l,4- or 1,5-naphtha~enedicar~oxylic acids. The preferred dicarboxylic acids are terephthalic acid or a mix~ure of terephthalic and isophthalic acids.
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2103~2~3 7 8C~5401 ~, ! ', Another useful high molec:ular weight polye~ter .may be derived from the reaction of either the cis- or .trans- isomer (or a mixture th~reof) of 1,4-cyclohexane-dimethanol with a mixture of isophthalic and terephthalic ~;5 acids. Such a polyester would have repeating units of the formula :
~ C
.. - 10 -- CH2 ~ CEI2-- O -- C ~d Still another useful high molec-llar weight polyester is a copolyester derived from a cyclohexanedimethanol, an alkylene glycol and an aromatic dicarboxylic acid. The~e copolyesters are prepared by ~: 15 condensing either the cis- or trans- isomer (or mixture thereof) of, for example, 1,4-cyclohexanedimethanol and .an alkylene glycol with an aromatic dlcarboxylic acid so - as to produce a copolyester having units of the formulae:
~' o o :i 20 --t--CH2 ~ ~ CH2-- - C--R c~x O O
:i t ~CH;~ ) n O -- C ~ R -- C~
,, `;, wherein the cyclohexane ring is selected from the cis-f and tran~- isomers thereof, R is as previously defined, 25 n is an integer of 2 to 6, the x units compris~ from about 10 to about 90 perc~nt by weight and the y units comprise from about 9G ~o about 10 percent by wsight.
Such copolyesters may be deriv~d from the ~' reac~ion of either ~he cis- or trans- isomer (or mixtures ;:130 thereof) of 1,4-cyclohexanedime~hanol and ethylene glycol ,iwith terephthalic acid in a molar ratio of 1:2:3. These copolyesters have repea~ing uni~s of the following formulae :
l 2~03~2~
: 8 8CV-5401 '''' --~0--CH~ CN2--0 -- C ~C~
'-". O ~ o ~0 ~CH2~ 0 -- C ~ C~
wherein x and y are as previously defined.
The high molecular weight polyesters described herein are either commercially available or can he produced by following me~hods well known in the art, such as those set forth in, for example, United States Patent Nos. 2,901,466, 2,465,319 and 3tO47,539-: Particularly suitable for practice of the present invention is high molecular weight PBT, which is sold coZ~merclally as VALOX~ 295 (melt viscosity of about 151100 poise) or V~LOX~ 315 (melt viscosity of about 8500 poise), both available from General Electric Company.
The PBT blend can comprise the low molecularweight PBT resin in amounts ranging from about 5 to about 95, preferably from about 20 to about 80, more preferably from about 30 to about 70 and most preferably from about 40 to about 60 parts by weight based on 100 total parts by weight of the low molecular weight PBT and high molecular weight polyestex resins ~aken together.
Accordingly, the PBT blend comprises the hi~h mole~ular weight polyester resin in amounts r~nging from about 35 to about 5, preferably from about 90 ~o about 10, more preferably from about 70 to about 30 and mos~ preferably from about 60 to about 40, pax~s by weight based on 100 total parts by weight of the low molecular weight PBT and high molecular weight polyester res~ns taken together.
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~:The phosphorus-containing stabilizers oP the present invention may comprise (i) acidic phosphate salts such as monozinc phosphates, sodium dihydrogen phosphate, ;potassium hydrogen phosphate, calcium hydrogen phosphate, sodium acid pyrophosphate and mixtures thereof. It has also been found that certain phosphil:e compounds (ii) may also be used in the practice of the present invention, e.g., those of the general formula P-(OR')3 wherein each R' is the same or different and independe~tly represents hydrogen, alkyl groups, aryl groups or any mixture thereof provided that at least one of the R' groups is hydrogen or alkyl. Illustratively, these include, but are not limited to, diphenylisodecyl phosphite, diisooctyl phosphite, dilauryl phosphite, diphenyl phosphite, phenyl diisodecyl phosphite, ethyl hexyl diphenyl phosphite, stearyl phosphite and mixtures thereof. The phosphorus-containing stabilizers may also comprise (iii) Group IB or Group IIB phosphate salts such as zinc phosphate or ~iv~ phosphorous oxo acids such as phosphorous acid, phosphoric acid, polyphosphoric acid, or hypophosphorous acid.
Preferred are phosphorus-containing compounds selected from zinc phosphate, diphenylisodecyl phosphite, monosodium phosphate and sodium acid pyrophosphate and mixtures thereof. Most preferred is zinc phosphate.
The phosphorus-containing compounds are generally employed in the compositions of the present inven~ion in amounts ranging from about 0.1 to about 10, preferably from about 0.1 to about 5, more preferably from about 0.1 to about 2 and most preferably from about 0.2 to about l, weight percent based on the weight of the total compoRition.
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The compositions of the present invention may also comprise other thermoplastic resins which are conventionally added to polyester resins. These may include resins such as polycarbonates, polyester-carbonates, polyarylates and mixtures thereof.
In other embodiments of the present invention, - the compositions can further comprise impact modifiers.
Particularly useful impact modifiers generally comprise rubbery impact modifiers. These are well known to those skilled in the art, and any of them normally employed with polyester resins may be employed herein.
The preferred impact modifiers generally comprise an acrylic or methacrylic grafted polymer of a ~ conjugated diene or an acrylate elastomer, alone, or ;- 15 copolymerized with a vinyl aromatic compound.
; Particularly useful are the core-shell polymers of the type available from Rohm & Haas, for example, those sold , under the trade designation Acryloid~. In general these impact modifiers contain units derived from butadiene or ` 20 isoprene, alone or in co~kination with a vinyl aromatic -. compound, or butyl acrylate, alone or in combination with a vinyl aromatic compound. The aforementioned impact modifiers are believed to be disclosed in Fromuth et al., United States Patent No. 4,180,494; Owens, United States ~;i 25 Pa~ent No. 3,808,180; Farnham et al., United S~a~es Patent No. 4,096,20~; and Cohen et al., United States ;.! Patent No. 4,260,693. Most preferably, the impact -3 modifier will comprise a two stage polymer having either a butadiene or butyl acxylate based rubbery core and a second stage polymerized from methylmethacrylate alone, or in combination with styrene. Also present in the . . , first stage are crosslinking and/or graftlinking ' monomers. Examples of the crosslinking monomers include - 1,3 butylene diacrylate, divinyl ben~ene and butylene dimethacrylate. Examples of graftlinking monomers are allyl acrylate, allyl methacryla~e and diallyl maleate.
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11 ~CY-5401 Additional preferred impact modi~ier~ are of the type disclosed in United States ]?atent No. 4,292,233.
These impact modifiers comprise, generally, a relatively high content of a cross-linked butacliene polymer grafted -5 base having grafted thereon acrylonitrile and styrene.
~Other suitable impact modifiers include, but -.~
are not limited to ethylene vinyl acetate, ethylene -ethylacrylate copolymers, SEBS (styrene ethylene-butylene styrene) and SBS (styrene-butadiene-styrene) block copolymers, EPDM (ethylene propylene diene monomer) an~
EPR (e~hylene propylene rubber) copolymers, etc. All of these are well known to those skilled in the art and are available commercially.
The compositions of the present invention may further contain one or more reinforcing agents including glass fibers. Typical reinforcing agents useful in the practice of the present invention include, but are not limited to, glass fiber, ~alc, mica, clay or combinations thereof.
The filamentous glass which may be employed a~
a reinforcing agent in the present compositions i~ well known to those skilled in the art and i5 widely availiable from a number of manufacturers. For compositions to be employed for electrical uses, it is 2S preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda-free. This is more commonly known as "E" glass.
However, other glasses are useful where electrical prop~ties are not so important, e.g., the low soda glass known as "C" glass. The filaments are made by s~andard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. The filament diameters generally range from about 0.00012 to 0.00075 inches but thls is not critical to the pre~ent invention.
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Further, the glass fibers useful in the practice of the present invention may also be treated with functionalized silicon compounds to improve interaction with the polymer matrix, as is well known to those skilled in the art. Functionalized silanes, especially alkoxy silanes may be useful in this regard.
Illustratively these include, but are not limited to, aminopropyl triethoxy silane, glycidyl propyl trimethoxy silane, ~3,4-epoxy cyclohexyl) ethyl triethoxy silane, mercaptopropyl silane, aminoethyl aminopropyl alkoxy silane, ureido-alkyl trialkoxy silane and mixtures of any of the foregoing.
The length of the glass fila~ents and whether or not they are bundled into fibers and the fibers bundled in ~urn to yarns, ropes or rovings, or woven into mats and the like are also not critical to the present invention. However, in preparing molding compositions it is convenient to use the filamentous glass in the form of chopped strands of from about 0.0125 ~o about 2 inches lony. In articles molded from the compositions on the other hand, even shorter lengths will ~e encountered due to fragmentation during compounding.
~, In general, the filamentous glass reinforcement comprises from about 2.5 to about 60% by weight based on the total weigh~ of the compositions of the present invention. It i~ more preferred ~hat the gla~s comprise from about 5 to about 55 and most preferred from about 20 to about 40~ by weight of the total weight of the composition.
The present invention may further comprise a flame retardant compound. ~ny of the conventional halogenated aromatic flame retardants such as decabromodiphenyl ether, brominated phthalimides, brominated polyphenylenc ethers, bromlne containlng !
~l :l i' 13 2 ~ 03 ~2~ 8CV-5401 ,,~
- polyacrylates or methacrylates, i.e., polypentabromo-benzyl acrylate and/or brominated st:yrene polymers can be employed in the present invention. These are well known to those skilled in the art and '~re described in the patent literature~ Preferred are derivatives of tetrabromo bisphenol A, sueh as its polycarbonate polymer or ~he polymer of its adduct with epichlorohydrin tbrominated phenoxy resin). They may be used alone, or in conjunction with a synergist, particularly inorganic or organic antimony compounds. Such compounds ar,e widely available or can be made in known ways. Especially preferred is antimony oxide.
Flame retardant embodiments of the present ; invention may further comprise a drip retardant agent to prevent dripping during burning. Such compounds are well known to those skilled in the art and include, but are not limited to, various fluorinated polyolefins.
Particularly useful is polytetrafluoroethylene ~PTFE).
See, e.g., Wambach, United States Patent No. 3,671,487.
The compositions of the present invention can also comprise a wide variety of other additives, such as ~ W stabilizers, pigments, colorants, fillers, - plasticizers, proces~ing aids, antioxidan$s and the like.
- Such components are added in effective amounts to impart the desired properties on the compositions of the presen~
invention for the specific application.
The method of blending the compositions of the present invention is not critical and can be carried out by conventional melt processing techniques. One convenient method comprises blending the P~T resins and other ingredients in powder or granular form, extruding the blend and comminuting into pellets or o~her suitable shapes. The ingredients are combined in any usual manner, e.g., by dry mixing or by mixing in the melted state in an extruder, on a heated mill or in other mixers.
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- An alternative method of blending can comprise preparing a preblend of the polyesters and then adding the other ingredients to the preblend. For exa~ple, a preblend of the PBT resins and stabilizer can be fed into the upstream port of an extruder with addition of the other ingredients such as glass fiber~ in a downstream port of the extruder.
In another embodiment, the various compounds can be precompounded, pelletized and then molded.
Precompounding can be carried sut in convQntional equipmen~. For example, a dry blend of the ingredientscan be fed into a single screw extruder, the screw having a long transition section to insure proper melting.
Alternatively, a twin screw extrusion machine can be fed with the resins and other additives at the feed port and reinforcements fed downstream. In either case, a i generally suitable machine temperature will be from about 450 to about 575F.
The precompounded composition can be extruded and cut or chopped into molding compounds, such as conventional granules, pellets, etc. by s~andard techniques.
~ ~he compositions can be molded in any equipment j conventionally used for thermoplastic compositions. For example, good results will be obtained in an injeckion molding machine, with conven~ional cylinder temperatures, e.g., 500F, and conventional mold temperatures, e.g., 150F.
, 30 DESCRIPTION O~ ~HE PREF RRED E~BODI~ENTS
The following examples are presented in order to illustrate the present invention. They are not to be construed to limit the scope of the appended claims in any manner whatsoever.
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,EXAMPLES l~3 '~The following examples demonstrate the US2 of various stabilizers in a polyester resin blend. The ".blends are prepared by tumble blending the ingredients i5 (parts by weight), extruding in a 2.5 inch vented single screw extruder with a melt tempera1:ure of 500 to 530F.
They are dried and molded on an 80 ton Van Dorn injection molding machine at a temperature of 500C, and a mold 'temperature of 150C. Kayness~ melt viscosity is measured by predrying the sample for 1 hour in a circulating oven at 150C and using a Kay~ess, Galaxy V
capillary rheometer with a melt temperature of 25QC, melt force of 150 lbs, and a shear rate of 400 sec l, Parallel plate rheology is measured using a Gottfert~
2001 rheometer with a parallel plate radius of 12.5 mm, a gap of 1.0 mm and a melt temperature of 250C with a -. 15% strain. The results along with compositional data ~ are set forth below in ~able 1.
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Example lA* 1 .2 3 Composition~ pbw PBT 295b 40 40 40 40 PBT 195 15 15 :L5 15 Gla~s fibersC 30 30 30 30 FRC 13.2 13.2 13.2 13.2 PTFEe f 1.25 1.25 :i.25 1.25 Irganox 1076 0.15 0.15 0.15 0.15 PE-l~g 0.2 0.2 1).2 0.2 DPDPn -- 0.2 -- __ znpL __ ---- O.Z
S~PP~ -- -- -- 0.2 Properties k Viscosity, poise : Rheology 1 minute 5434 4509 4201 5434 ; 15 minutes 7647 6649 6325 6375 : % increase 41 47 51 17 30 minutes 14610 7423 7099 124S0 % increase 169 64 69 129 * = Comparative Example : b = Valox~ 295, General Electric Company, 1100 poise = Valox ~ 195, General Electric Company, 300 poise d = OCF 183E, K filament glass, Owens Corning Fiberylass : = Flame retardant concentrate of brominated :: polycarbonate, antimony oxide, and a polymer binder f = Polytetr~f}uoroethylene resin dispersion = An~ioxidant, Ciba-Geigy Company = Pentaerythritol tetrastearate i = Diphenylisodecyl phosphite, GE Specialty Chemical inc phosphate, Alfa Ch~mical Company = Sodium acid pyrophosphate = Measured by parallel plate rheology at 250C
A time sweep of the melt viscosity for the above examples is shown in Figure 2. It can be seen that the compositions stabilized with DPDP, ZnP and SAPP
exhibit significantly improved melt viscosity stability over the control example.
i 2 ~ 2 0 : 17 8CV-5401 .., ~ EXAMPLES 4-5 -The procedure of Example 1 is generally followed to illustrate the eff~ectiveness of zinc - phosphate as a melt stabilizer in polyester blends. The results, along with compositional data are set forth in Table 2 below.
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Exam~le 4A* 4 5A* 5 Composition, pbw PBT 195a 50 49.8 50 49.8 PBT 295 50 49.8 PBTd315 -- -- 50 49.8 : ZnP -- 0.4 -- 0.4 Properties - Viscosity~ poise : Kayene~s T105 52~ 544 1303 1439 - Rheology 1 minute581 610 1589 1868 . 15 minute 756 576 1554 1530 % increase 30 10.8 -2 -18 30 minute 1109 874 1891 1534 % increase 91 43 19 -12.5 * = Comparative example , b = Valox~ 195, General Electric Company, 300 poise I = Valox~ 295, General Electric Company, 1100 poi3e c = Valox~ 315, General Electric Company, 8500 poise d = Zinc phosphate, Zn3(PO4)2-2H2O, Alpha Chem. Co.
f = at 250C, poise - dwell time, 5 minutes = dwell time, 10 minutes h = Parallel plate rheology, viscosity V5. time at 250C
poise, ~ viscosity increase from 1 minute It can be seen from the da~a in Table 2 that , zinc phosphate prevents build up of melt viscosity in the ¦ polyester blends, exhibiting a signi~icant improvement in maintaining a consistent melt visc05ity over time.
., 210~A2~U
.. 18 8CV-5401 :,.
,!~,''. The procedure of Example 1 is followed to compare the effectiveness of zinc phosphate stabilizer over other stabilizers. The results, along with compositional dAta are set forth below in Table 3.
.
Example 6A* 6B* 6C* 6 Composition, pbw PBT 295b 40.2 40.2 40.2 40.2 PBT 195 15.0 15. a 15.0 15.0 Glass FibersC 30.0 30.0 30.0 30.0 FRCa 13.2 13.2 13.2 13.2 PTFEe f 1.25 1.25 1.25 1.25 Irganox 1076 0.15 0.15 0.15 0.15 PE-18g 0.20 0.20 0.20 0.20 :: Irgafos 168h -- 0.20 -- --, TPPP -- -- 0.20 --ZnP~ -- -- -- 0.20 Properties - Viscosity~ poise ,i Kayene~s :i T5 2995 3290 3380 2200 ~ T10m 3311 4144 3411 2149 ','.7 Rheology , poise ;i. 1 min5183 4636 4414 4044 I 15 min 10910 7112 7718 5165 .-. % 110 53.4 75 2 30 min 11840 9853 8445 5644 % 128 112 91 40 ~ * = Comparative Example :, b = Valox~ 295, General Elec~ric Company, 1100 poise = Valox~ 195, General Electric Company, 300 poi~e ' d = OCF 183E, K filament glass, Owens Corning Fiberglass .~ = Flame retardant concentrate, PPG Industries ', f = Polytetrafluoroethylene concentrate i = Antioxidant, Ciba Geigy Company ' g = Pentaerythritol tetrastearate .i i = Tris(2,4-di-t-butylphenyl)phosphite, Ciba Geigy Co.
3 . = Tetrapotassium pyrophosphate = Zinc phosphate, ~n3(PO4)2 2H2O, Alpha Chem. Co.
= at 250C, po~se ~, l = dwell time, 5 minutes = dwell time, 10 minutes n = Parallel plate rheology, viscosity vs. time at 250C
= % viscosity increase from l minute ~' `` 2~42~
Table 3 above clearly demonstrates the improvements in melt viscosity stability obtained with the stabilizers of the present invention. The parallel plate rheology shows a 100% increase in melt viscosity in compositions stabilized with other phosphorus-containing additives, Examples 6A*-6C*, while the composition stabilized according to the present invention exhibits less than 50% increase in melt viscosity. Further, the Kayeness data highlights the viscosity increases for the compositions containing other phosphorus-containing additives.
;~ EXAMPLE 7 `:
The procedure of Example 1 is generally followed to observe the melt viscosity stability of unfilled polyester blends with various stabilizers. The j results, along with compositional data are set forth below in Table 4.
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:
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Example 7A* 7B* 7 Composition, pbw PBT 295a 50.0 49.8 49.8 PBT l9S~ 50.0 49.8 49.8 Irg~fos~ 168C -- 0.4 --~- ZnP -_ __ 0.4 Properties : Viscosit~, poise : Kayenes~
: Ts 539 544 577 TlOg 513 508 544 Rheology 1 min 607 590 610 15 min 828 812 676 . 30 min 1197 1114 874 %l 97 89 43 a* = Comparative Example ::~= Valox~ 295/ General Electric Company, 1100 poise ~b = Valox~ 195, General Electric Co~pany, 300 poise .:= Tris(2,4-di-t-butylph~nyl)phosphite, Ciba Geigy Co.
;~d = Zinc phosphate, Zn3(PO4)2 2H2O~ Alp = at 250C, poise f = dwell time, 5 minutes g = dwell time, 10 minutes h = Parallel plate rheology, viscosity vs. time at 2~0C
1 = ~ viscosity incxease from 1 minute . .
The data in Table 4 demonstrates the significant improvements obtained according to the present invention in unfilled PB~ blends.
~XAMPLE5 8-13 ' ~The procedure of Example 1 is generally ''~followed, except employing further stabilizers. The results, along with compositional da~a are set forth below in Table 5O
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The data in Table 5 show the improvements in ; melt viscosity stability provided by compositions of the present invention.
:;' EXAMPLES l~-l9 :, 5The procedure of Example 1 is generally followed, except employing blends of the low molecular weight PBT wikh polycarbonate in a non-flame retardant system. The results, along with compositional flata are set forth below in Table 6.
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The above-mentioned patents and test methods - are all hereby incorporated by reference.
:. Many variations of the present invention will suggest thems~lves to those of ordinary skill in ~he art in light of the above-detailed description. Conventional . additives such as clay, mica, piyments and colorants can -. be added in conventional amounts. Other phosphite :~ stabilizers such as diisooctyl phosphite, trilauryl :~ phosphite, diphenyl phosphite, phenyl diisodecyl .. 10 phosphite, ethyl hexyl diphenylphosphite and stearyl -- phosphite may be employed. Further, the compositions can include a wide variety of other thermoplas~ic resins such as polycarbonates, polyarylates, polyester carbonates and mixtures thereof; as well as a variety of impact modifers such as core-shell polymers, ethylene vinyl ~cetate, :. ethylene ethylacrylate copolymer, SEBS, SBS, ERDM and EPR. All such obvious variations are within the full ~ntended scope of the appended clalms.
''
. 2 ~CV-5401 However, a problem which many pla tics operators have exprienced with high molecular weight polyesters is the di~ficulty in processiny the resins.
In response thereto, a relatively low molecular weight PBT, less than about 600 poise, as measured using a Tinius Olsen melt ind~xer at 250C', 0.042 inch orifice (ASTM method D-1238~ has been added to the high molecular weight polyester to provide improved flow blends which ~ still retain the exc~llent propertie~ of the high - 10 moleculax weight polyester. Howevex, it has been found that while the blends of high molecular weight polyester and low molecular weight PBT initially exhibit a decrease in melt viscosity, the melt viscosity builds over time.
; See Figure 1. Such a build up of viscosity of the blends limits the use of low molecular weight PBT in commercial `; applications. It would therefore represent a notable advance in the state of the art if a more stable high . flow blend of a high molecular weight polyester and low - molecular weiyht PBT could be found.
Jacquiss et al., United States Patent No.
4,532,290, teach stabilizing polycarbonate-polyester compositions against undesirable changes in melting point by adding monosodium phosphate and/or monopotassium phosphate to the compositions. Hepp, United States Patent No. 4,687,802, discloses that the arc track rate of PBT resins can be improved by the addition of a metal ~, salt to the PBT resin.
However, none of the prior art teachings suggests a method of preparing a stable high flow blend of a hiyh molecular weight polyester and a low molecular weight PBT. Surprisingly, the present inventor has now found that if certain phosphorus-oontaining compounds are added to the blends of high molecular weight polyester ;~ and low molecular weight P~T, there is achieved a high flow blend having excellent melt stability.
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--2~03~20 ~3CV-5401 BRIEF DESCRIPTION OF T~E DRAWNINGS
..
FIGURE 1 depicts in graphic form a comparison of a time sweep of the melt viscosity of an unstabilized blend of a high molecular weight PBT (1100 poise) resin and a low molecular weight (300 poise) PBT resin (Line A) against a time sweep of a high molecular we~gh~ PBT resin : (Line B).
FIGURE 2 depicts in graphic form a comparison of time sweeps of blends of high molecular weight PBT
. 10 and low molecular weight PBT with various additives from A the data set forth in Table 1 hereinbelow.
SUMMARY OF THE PRESENT INVENTION
According to the present invention there is disclosed~a ~hermoplastic resin blend comprising~ ~a) a relatively low molecular weight polybutylene terephthalate resin; (b) a relatively high molecular weight polyester resin; and (c) an effective melt viscosi~y s~abilizing amount of (i) an acidic pho~phate salt, til) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl qroup, (iii) a Group IB or IIB metal phosphate salt (iv) a phosphorous oxo aci~ or . (v) a mixture of any of the foregoing.
:~, Also according to the present invention there is pro~ided a process for stabilizing the melt viscosity of a thermoplastic resin blend comprising a relatively low molecular weigh~ PBT resin and a relatively high molecular weight polyester resin comprising adding to the blend an ~ffective amount of a (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl group, (iii) a Group IB or IIB metal phosphate salt (iv) a phosphorous oxo acid or (v) a mixtuxe of any of the foregoing.
.. . .
21~3~20 4 ~CV-5401 ' DETAILED DESCRIPTION OF THE PFIESE?IT INVENTION
The low molecular weight polybutylene terephthalate (PB~) useful in the practice of the present invention is a PBT resin having a melt viscosity of less than 600 poise, more prefexably less than about 450 -. poise, and most preferably less than about 300 poise.
~`~ The high molecular weight polyester resins useful in the practice of the present invention are polyester resins having a melt viscosity above about 600 poise, more preferably above about 900 poise, and mos~
preferably above about 1100 poise~ Preferred as the high molecular weight polyester resins are high molecular weight polybutylene terephthalate, polyethylene :, terephthalate and polycyclohexane dimethylene : 15 terephthalate.
The low molecular weight polybutylene tereph halate resin employed in the present invention is typically one obtained by polymerizing a glycol component at least 70 mol %, preferably at least 80 mol %, of which comprises a tetramethylene glycol; and an acid component at least 70 mol %, preferably at least 80 mol %, of which comprises terephthalic acid/ and polyester-forming deriva~ives thereof. Particularly us~ful is poly(l,4-butylene terephthalate).
Prefer~bly) the glycol does not contain more than 30 mol %, more preferably not more than 20 mol %, of another glycol, such as ethylene glycol, trimethylene glycol, 2-methyl-1,3-propane glycol, hexamethylene glycol, decam~thylene glycol, cyclohexane dimethanol, or neopentylene glycol. Examples of o~her copolycondensable polyols include 1,3-propylene glycol, pentaerythritol, 1,6-hexanediol, polyethylene glycol and polytetra-methylene glycol.
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Preferably the acid component contains no~ more than 30 mol %, more preferably not nnore than 20 mol %, of : another acid such as isophthalic acid, 2,6-, . .
..naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic .5 acid, 1,5-naphthalenedicarboxylic acid, 4,4'-diphenyl-dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, ~:p-hydroxy benzoic acid, sebacic acid, adipic acid and ,'T,,polyester-forming derivatives thereof. Examples of other ,~copolycondensable polycarboxylic acidis include azelaic 5"10 acid, dodecane dicarboxylic acid, trimellitic acid, trimesic acid and hexahydroterephthalic acid.
~;.The low molecular weight PBT resin~ can be ~.prepared according to methods known to those of ordinary !''skill in the art, or they may he obtained commercially.
15 Low molecular weight PBT is VALOX~ 195 having a melt viscosity of about 300 poise from General Electric `~ Company.
The high molecular weight polyester resins are those which are prepared in similar ma~ner to the low 20 molecular weight PBT, i.e., by polymerizing a glycol ,component and an acid componen~. Typically they are .~derived from an aliphatic or cycloalipha~ic ~iol, or ,mixture~ thereof, containing from 2 to about 10 carbon -atoms and at lea~t one aromatic dicarboxylic acid.
25 Preferred polyes~ers ar~ derived from an alipha~ic diol :~and an aromatic dicarboxylic acid and have repeating -~units of the ollo~ing general formula :
,- O
,, 1~
; 30 -t-CH2 ~ 0 - C ~ C
-;~ wherein n is an integer of fro~ 2 to 6. The most ~i preferred polyesters are poly(ethylene terephthalate), poly(l~4-butylene terephthalate) and mixtures thereof.
.; .
~3~20 6 8~V-5401 Al~o contemplated for Us~! herein as the high molecular weight polyesters, are the above polyesters with minor amounts, e.g., from 0.5 to about 5 percent by weight, of units derived from aliphatic acids and/or aliphatic polyols to form copolyesters. The aliphatic polyols include glycols, such as poly(ethylene glycol).
All such polyesters can be made following the teachings of, for example, United States Pat~nt Nos. 2,465,319 and 3,047,539.
Also useful as the high molecular weight polyesters are those derived from a cycloaliphatic diol and an aromatic dicarboxylic acid and which are prepared, for example, by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-cyclohexanedimethanol with an aromatic dicarboxylic acid so as to produce a polye ter having recurring units of the following formula:
O O
--O -- CH2 0 CH2--O-- C ~ C
., ~0 wherein the cyclohexane ring is selected Prom the Ci5-and trans- iso~rs thereof and R represents an aryl radical containing from 6 to about 20 carbon atoms and which is the decarboxylated re~idue derived from an aromatic dicarboxylic acid.
. Examples of arom~tic dicarboxylic acids I represented by ~he decarboxylated residue R are isophthalic or terephthalic acid, 1,2-di-~p-. carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl etherS etc., and mixtures of the~e. All o these acids contain at l ast on~ aromatic nucleu~. Acids containing fused rings can also be present, such as in l,4- or 1,5-naphtha~enedicar~oxylic acids. The preferred dicarboxylic acids are terephthalic acid or a mix~ure of terephthalic and isophthalic acids.
~.
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2103~2~3 7 8C~5401 ~, ! ', Another useful high molec:ular weight polye~ter .may be derived from the reaction of either the cis- or .trans- isomer (or a mixture th~reof) of 1,4-cyclohexane-dimethanol with a mixture of isophthalic and terephthalic ~;5 acids. Such a polyester would have repeating units of the formula :
~ C
.. - 10 -- CH2 ~ CEI2-- O -- C ~d Still another useful high molec-llar weight polyester is a copolyester derived from a cyclohexanedimethanol, an alkylene glycol and an aromatic dicarboxylic acid. The~e copolyesters are prepared by ~: 15 condensing either the cis- or trans- isomer (or mixture thereof) of, for example, 1,4-cyclohexanedimethanol and .an alkylene glycol with an aromatic dlcarboxylic acid so - as to produce a copolyester having units of the formulae:
~' o o :i 20 --t--CH2 ~ ~ CH2-- - C--R c~x O O
:i t ~CH;~ ) n O -- C ~ R -- C~
,, `;, wherein the cyclohexane ring is selected from the cis-f and tran~- isomers thereof, R is as previously defined, 25 n is an integer of 2 to 6, the x units compris~ from about 10 to about 90 perc~nt by weight and the y units comprise from about 9G ~o about 10 percent by wsight.
Such copolyesters may be deriv~d from the ~' reac~ion of either ~he cis- or trans- isomer (or mixtures ;:130 thereof) of 1,4-cyclohexanedime~hanol and ethylene glycol ,iwith terephthalic acid in a molar ratio of 1:2:3. These copolyesters have repea~ing uni~s of the following formulae :
l 2~03~2~
: 8 8CV-5401 '''' --~0--CH~ CN2--0 -- C ~C~
'-". O ~ o ~0 ~CH2~ 0 -- C ~ C~
wherein x and y are as previously defined.
The high molecular weight polyesters described herein are either commercially available or can he produced by following me~hods well known in the art, such as those set forth in, for example, United States Patent Nos. 2,901,466, 2,465,319 and 3tO47,539-: Particularly suitable for practice of the present invention is high molecular weight PBT, which is sold coZ~merclally as VALOX~ 295 (melt viscosity of about 151100 poise) or V~LOX~ 315 (melt viscosity of about 8500 poise), both available from General Electric Company.
The PBT blend can comprise the low molecularweight PBT resin in amounts ranging from about 5 to about 95, preferably from about 20 to about 80, more preferably from about 30 to about 70 and most preferably from about 40 to about 60 parts by weight based on 100 total parts by weight of the low molecular weight PBT and high molecular weight polyestex resins ~aken together.
Accordingly, the PBT blend comprises the hi~h mole~ular weight polyester resin in amounts r~nging from about 35 to about 5, preferably from about 90 ~o about 10, more preferably from about 70 to about 30 and mos~ preferably from about 60 to about 40, pax~s by weight based on 100 total parts by weight of the low molecular weight PBT and high molecular weight polyester res~ns taken together.
i <
21~342~
.' .
~:The phosphorus-containing stabilizers oP the present invention may comprise (i) acidic phosphate salts such as monozinc phosphates, sodium dihydrogen phosphate, ;potassium hydrogen phosphate, calcium hydrogen phosphate, sodium acid pyrophosphate and mixtures thereof. It has also been found that certain phosphil:e compounds (ii) may also be used in the practice of the present invention, e.g., those of the general formula P-(OR')3 wherein each R' is the same or different and independe~tly represents hydrogen, alkyl groups, aryl groups or any mixture thereof provided that at least one of the R' groups is hydrogen or alkyl. Illustratively, these include, but are not limited to, diphenylisodecyl phosphite, diisooctyl phosphite, dilauryl phosphite, diphenyl phosphite, phenyl diisodecyl phosphite, ethyl hexyl diphenyl phosphite, stearyl phosphite and mixtures thereof. The phosphorus-containing stabilizers may also comprise (iii) Group IB or Group IIB phosphate salts such as zinc phosphate or ~iv~ phosphorous oxo acids such as phosphorous acid, phosphoric acid, polyphosphoric acid, or hypophosphorous acid.
Preferred are phosphorus-containing compounds selected from zinc phosphate, diphenylisodecyl phosphite, monosodium phosphate and sodium acid pyrophosphate and mixtures thereof. Most preferred is zinc phosphate.
The phosphorus-containing compounds are generally employed in the compositions of the present inven~ion in amounts ranging from about 0.1 to about 10, preferably from about 0.1 to about 5, more preferably from about 0.1 to about 2 and most preferably from about 0.2 to about l, weight percent based on the weight of the total compoRition.
2103~21~
The compositions of the present invention may also comprise other thermoplastic resins which are conventionally added to polyester resins. These may include resins such as polycarbonates, polyester-carbonates, polyarylates and mixtures thereof.
In other embodiments of the present invention, - the compositions can further comprise impact modifiers.
Particularly useful impact modifiers generally comprise rubbery impact modifiers. These are well known to those skilled in the art, and any of them normally employed with polyester resins may be employed herein.
The preferred impact modifiers generally comprise an acrylic or methacrylic grafted polymer of a ~ conjugated diene or an acrylate elastomer, alone, or ;- 15 copolymerized with a vinyl aromatic compound.
; Particularly useful are the core-shell polymers of the type available from Rohm & Haas, for example, those sold , under the trade designation Acryloid~. In general these impact modifiers contain units derived from butadiene or ` 20 isoprene, alone or in co~kination with a vinyl aromatic -. compound, or butyl acrylate, alone or in combination with a vinyl aromatic compound. The aforementioned impact modifiers are believed to be disclosed in Fromuth et al., United States Patent No. 4,180,494; Owens, United States ~;i 25 Pa~ent No. 3,808,180; Farnham et al., United S~a~es Patent No. 4,096,20~; and Cohen et al., United States ;.! Patent No. 4,260,693. Most preferably, the impact -3 modifier will comprise a two stage polymer having either a butadiene or butyl acxylate based rubbery core and a second stage polymerized from methylmethacrylate alone, or in combination with styrene. Also present in the . . , first stage are crosslinking and/or graftlinking ' monomers. Examples of the crosslinking monomers include - 1,3 butylene diacrylate, divinyl ben~ene and butylene dimethacrylate. Examples of graftlinking monomers are allyl acrylate, allyl methacryla~e and diallyl maleate.
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21~3~2~
11 ~CY-5401 Additional preferred impact modi~ier~ are of the type disclosed in United States ]?atent No. 4,292,233.
These impact modifiers comprise, generally, a relatively high content of a cross-linked butacliene polymer grafted -5 base having grafted thereon acrylonitrile and styrene.
~Other suitable impact modifiers include, but -.~
are not limited to ethylene vinyl acetate, ethylene -ethylacrylate copolymers, SEBS (styrene ethylene-butylene styrene) and SBS (styrene-butadiene-styrene) block copolymers, EPDM (ethylene propylene diene monomer) an~
EPR (e~hylene propylene rubber) copolymers, etc. All of these are well known to those skilled in the art and are available commercially.
The compositions of the present invention may further contain one or more reinforcing agents including glass fibers. Typical reinforcing agents useful in the practice of the present invention include, but are not limited to, glass fiber, ~alc, mica, clay or combinations thereof.
The filamentous glass which may be employed a~
a reinforcing agent in the present compositions i~ well known to those skilled in the art and i5 widely availiable from a number of manufacturers. For compositions to be employed for electrical uses, it is 2S preferred to use fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda-free. This is more commonly known as "E" glass.
However, other glasses are useful where electrical prop~ties are not so important, e.g., the low soda glass known as "C" glass. The filaments are made by s~andard processes, e.g., by steam or air blowing, flame blowing and mechanical pulling. The filament diameters generally range from about 0.00012 to 0.00075 inches but thls is not critical to the pre~ent invention.
:
:
2~03~2~
Further, the glass fibers useful in the practice of the present invention may also be treated with functionalized silicon compounds to improve interaction with the polymer matrix, as is well known to those skilled in the art. Functionalized silanes, especially alkoxy silanes may be useful in this regard.
Illustratively these include, but are not limited to, aminopropyl triethoxy silane, glycidyl propyl trimethoxy silane, ~3,4-epoxy cyclohexyl) ethyl triethoxy silane, mercaptopropyl silane, aminoethyl aminopropyl alkoxy silane, ureido-alkyl trialkoxy silane and mixtures of any of the foregoing.
The length of the glass fila~ents and whether or not they are bundled into fibers and the fibers bundled in ~urn to yarns, ropes or rovings, or woven into mats and the like are also not critical to the present invention. However, in preparing molding compositions it is convenient to use the filamentous glass in the form of chopped strands of from about 0.0125 ~o about 2 inches lony. In articles molded from the compositions on the other hand, even shorter lengths will ~e encountered due to fragmentation during compounding.
~, In general, the filamentous glass reinforcement comprises from about 2.5 to about 60% by weight based on the total weigh~ of the compositions of the present invention. It i~ more preferred ~hat the gla~s comprise from about 5 to about 55 and most preferred from about 20 to about 40~ by weight of the total weight of the composition.
The present invention may further comprise a flame retardant compound. ~ny of the conventional halogenated aromatic flame retardants such as decabromodiphenyl ether, brominated phthalimides, brominated polyphenylenc ethers, bromlne containlng !
~l :l i' 13 2 ~ 03 ~2~ 8CV-5401 ,,~
- polyacrylates or methacrylates, i.e., polypentabromo-benzyl acrylate and/or brominated st:yrene polymers can be employed in the present invention. These are well known to those skilled in the art and '~re described in the patent literature~ Preferred are derivatives of tetrabromo bisphenol A, sueh as its polycarbonate polymer or ~he polymer of its adduct with epichlorohydrin tbrominated phenoxy resin). They may be used alone, or in conjunction with a synergist, particularly inorganic or organic antimony compounds. Such compounds ar,e widely available or can be made in known ways. Especially preferred is antimony oxide.
Flame retardant embodiments of the present ; invention may further comprise a drip retardant agent to prevent dripping during burning. Such compounds are well known to those skilled in the art and include, but are not limited to, various fluorinated polyolefins.
Particularly useful is polytetrafluoroethylene ~PTFE).
See, e.g., Wambach, United States Patent No. 3,671,487.
The compositions of the present invention can also comprise a wide variety of other additives, such as ~ W stabilizers, pigments, colorants, fillers, - plasticizers, proces~ing aids, antioxidan$s and the like.
- Such components are added in effective amounts to impart the desired properties on the compositions of the presen~
invention for the specific application.
The method of blending the compositions of the present invention is not critical and can be carried out by conventional melt processing techniques. One convenient method comprises blending the P~T resins and other ingredients in powder or granular form, extruding the blend and comminuting into pellets or o~her suitable shapes. The ingredients are combined in any usual manner, e.g., by dry mixing or by mixing in the melted state in an extruder, on a heated mill or in other mixers.
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:
2~0~20 : 14 8CV-5401 '~:
- An alternative method of blending can comprise preparing a preblend of the polyesters and then adding the other ingredients to the preblend. For exa~ple, a preblend of the PBT resins and stabilizer can be fed into the upstream port of an extruder with addition of the other ingredients such as glass fiber~ in a downstream port of the extruder.
In another embodiment, the various compounds can be precompounded, pelletized and then molded.
Precompounding can be carried sut in convQntional equipmen~. For example, a dry blend of the ingredientscan be fed into a single screw extruder, the screw having a long transition section to insure proper melting.
Alternatively, a twin screw extrusion machine can be fed with the resins and other additives at the feed port and reinforcements fed downstream. In either case, a i generally suitable machine temperature will be from about 450 to about 575F.
The precompounded composition can be extruded and cut or chopped into molding compounds, such as conventional granules, pellets, etc. by s~andard techniques.
~ ~he compositions can be molded in any equipment j conventionally used for thermoplastic compositions. For example, good results will be obtained in an injeckion molding machine, with conven~ional cylinder temperatures, e.g., 500F, and conventional mold temperatures, e.g., 150F.
, 30 DESCRIPTION O~ ~HE PREF RRED E~BODI~ENTS
The following examples are presented in order to illustrate the present invention. They are not to be construed to limit the scope of the appended claims in any manner whatsoever.
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,EXAMPLES l~3 '~The following examples demonstrate the US2 of various stabilizers in a polyester resin blend. The ".blends are prepared by tumble blending the ingredients i5 (parts by weight), extruding in a 2.5 inch vented single screw extruder with a melt tempera1:ure of 500 to 530F.
They are dried and molded on an 80 ton Van Dorn injection molding machine at a temperature of 500C, and a mold 'temperature of 150C. Kayness~ melt viscosity is measured by predrying the sample for 1 hour in a circulating oven at 150C and using a Kay~ess, Galaxy V
capillary rheometer with a melt temperature of 25QC, melt force of 150 lbs, and a shear rate of 400 sec l, Parallel plate rheology is measured using a Gottfert~
2001 rheometer with a parallel plate radius of 12.5 mm, a gap of 1.0 mm and a melt temperature of 250C with a -. 15% strain. The results along with compositional data ~ are set forth below in ~able 1.
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Example lA* 1 .2 3 Composition~ pbw PBT 295b 40 40 40 40 PBT 195 15 15 :L5 15 Gla~s fibersC 30 30 30 30 FRC 13.2 13.2 13.2 13.2 PTFEe f 1.25 1.25 :i.25 1.25 Irganox 1076 0.15 0.15 0.15 0.15 PE-l~g 0.2 0.2 1).2 0.2 DPDPn -- 0.2 -- __ znpL __ ---- O.Z
S~PP~ -- -- -- 0.2 Properties k Viscosity, poise : Rheology 1 minute 5434 4509 4201 5434 ; 15 minutes 7647 6649 6325 6375 : % increase 41 47 51 17 30 minutes 14610 7423 7099 124S0 % increase 169 64 69 129 * = Comparative Example : b = Valox~ 295, General Electric Company, 1100 poise = Valox ~ 195, General Electric Company, 300 poise d = OCF 183E, K filament glass, Owens Corning Fiberylass : = Flame retardant concentrate of brominated :: polycarbonate, antimony oxide, and a polymer binder f = Polytetr~f}uoroethylene resin dispersion = An~ioxidant, Ciba-Geigy Company = Pentaerythritol tetrastearate i = Diphenylisodecyl phosphite, GE Specialty Chemical inc phosphate, Alfa Ch~mical Company = Sodium acid pyrophosphate = Measured by parallel plate rheology at 250C
A time sweep of the melt viscosity for the above examples is shown in Figure 2. It can be seen that the compositions stabilized with DPDP, ZnP and SAPP
exhibit significantly improved melt viscosity stability over the control example.
i 2 ~ 2 0 : 17 8CV-5401 .., ~ EXAMPLES 4-5 -The procedure of Example 1 is generally followed to illustrate the eff~ectiveness of zinc - phosphate as a melt stabilizer in polyester blends. The results, along with compositional data are set forth in Table 2 below.
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Exam~le 4A* 4 5A* 5 Composition, pbw PBT 195a 50 49.8 50 49.8 PBT 295 50 49.8 PBTd315 -- -- 50 49.8 : ZnP -- 0.4 -- 0.4 Properties - Viscosity~ poise : Kayene~s T105 52~ 544 1303 1439 - Rheology 1 minute581 610 1589 1868 . 15 minute 756 576 1554 1530 % increase 30 10.8 -2 -18 30 minute 1109 874 1891 1534 % increase 91 43 19 -12.5 * = Comparative example , b = Valox~ 195, General Electric Company, 300 poise I = Valox~ 295, General Electric Company, 1100 poi3e c = Valox~ 315, General Electric Company, 8500 poise d = Zinc phosphate, Zn3(PO4)2-2H2O, Alpha Chem. Co.
f = at 250C, poise - dwell time, 5 minutes = dwell time, 10 minutes h = Parallel plate rheology, viscosity V5. time at 250C
poise, ~ viscosity increase from 1 minute It can be seen from the da~a in Table 2 that , zinc phosphate prevents build up of melt viscosity in the ¦ polyester blends, exhibiting a signi~icant improvement in maintaining a consistent melt visc05ity over time.
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.. 18 8CV-5401 :,.
,!~,''. The procedure of Example 1 is followed to compare the effectiveness of zinc phosphate stabilizer over other stabilizers. The results, along with compositional dAta are set forth below in Table 3.
.
Example 6A* 6B* 6C* 6 Composition, pbw PBT 295b 40.2 40.2 40.2 40.2 PBT 195 15.0 15. a 15.0 15.0 Glass FibersC 30.0 30.0 30.0 30.0 FRCa 13.2 13.2 13.2 13.2 PTFEe f 1.25 1.25 1.25 1.25 Irganox 1076 0.15 0.15 0.15 0.15 PE-18g 0.20 0.20 0.20 0.20 :: Irgafos 168h -- 0.20 -- --, TPPP -- -- 0.20 --ZnP~ -- -- -- 0.20 Properties - Viscosity~ poise ,i Kayene~s :i T5 2995 3290 3380 2200 ~ T10m 3311 4144 3411 2149 ','.7 Rheology , poise ;i. 1 min5183 4636 4414 4044 I 15 min 10910 7112 7718 5165 .-. % 110 53.4 75 2 30 min 11840 9853 8445 5644 % 128 112 91 40 ~ * = Comparative Example :, b = Valox~ 295, General Elec~ric Company, 1100 poise = Valox~ 195, General Electric Company, 300 poi~e ' d = OCF 183E, K filament glass, Owens Corning Fiberglass .~ = Flame retardant concentrate, PPG Industries ', f = Polytetrafluoroethylene concentrate i = Antioxidant, Ciba Geigy Company ' g = Pentaerythritol tetrastearate .i i = Tris(2,4-di-t-butylphenyl)phosphite, Ciba Geigy Co.
3 . = Tetrapotassium pyrophosphate = Zinc phosphate, ~n3(PO4)2 2H2O, Alpha Chem. Co.
= at 250C, po~se ~, l = dwell time, 5 minutes = dwell time, 10 minutes n = Parallel plate rheology, viscosity vs. time at 250C
= % viscosity increase from l minute ~' `` 2~42~
Table 3 above clearly demonstrates the improvements in melt viscosity stability obtained with the stabilizers of the present invention. The parallel plate rheology shows a 100% increase in melt viscosity in compositions stabilized with other phosphorus-containing additives, Examples 6A*-6C*, while the composition stabilized according to the present invention exhibits less than 50% increase in melt viscosity. Further, the Kayeness data highlights the viscosity increases for the compositions containing other phosphorus-containing additives.
;~ EXAMPLE 7 `:
The procedure of Example 1 is generally followed to observe the melt viscosity stability of unfilled polyester blends with various stabilizers. The j results, along with compositional data are set forth below in Table 4.
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Example 7A* 7B* 7 Composition, pbw PBT 295a 50.0 49.8 49.8 PBT l9S~ 50.0 49.8 49.8 Irg~fos~ 168C -- 0.4 --~- ZnP -_ __ 0.4 Properties : Viscosit~, poise : Kayenes~
: Ts 539 544 577 TlOg 513 508 544 Rheology 1 min 607 590 610 15 min 828 812 676 . 30 min 1197 1114 874 %l 97 89 43 a* = Comparative Example ::~= Valox~ 295/ General Electric Company, 1100 poise ~b = Valox~ 195, General Electric Co~pany, 300 poise .:= Tris(2,4-di-t-butylph~nyl)phosphite, Ciba Geigy Co.
;~d = Zinc phosphate, Zn3(PO4)2 2H2O~ Alp = at 250C, poise f = dwell time, 5 minutes g = dwell time, 10 minutes h = Parallel plate rheology, viscosity vs. time at 2~0C
1 = ~ viscosity incxease from 1 minute . .
The data in Table 4 demonstrates the significant improvements obtained according to the present invention in unfilled PB~ blends.
~XAMPLE5 8-13 ' ~The procedure of Example 1 is generally ''~followed, except employing further stabilizers. The results, along with compositional da~a are set forth below in Table 5O
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The data in Table 5 show the improvements in ; melt viscosity stability provided by compositions of the present invention.
:;' EXAMPLES l~-l9 :, 5The procedure of Example 1 is generally followed, except employing blends of the low molecular weight PBT wikh polycarbonate in a non-flame retardant system. The results, along with compositional flata are set forth below in Table 6.
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The above-mentioned patents and test methods - are all hereby incorporated by reference.
:. Many variations of the present invention will suggest thems~lves to those of ordinary skill in ~he art in light of the above-detailed description. Conventional . additives such as clay, mica, piyments and colorants can -. be added in conventional amounts. Other phosphite :~ stabilizers such as diisooctyl phosphite, trilauryl :~ phosphite, diphenyl phosphite, phenyl diisodecyl .. 10 phosphite, ethyl hexyl diphenylphosphite and stearyl -- phosphite may be employed. Further, the compositions can include a wide variety of other thermoplas~ic resins such as polycarbonates, polyarylates, polyester carbonates and mixtures thereof; as well as a variety of impact modifers such as core-shell polymers, ethylene vinyl ~cetate, :. ethylene ethylacrylate copolymer, SEBS, SBS, ERDM and EPR. All such obvious variations are within the full ~ntended scope of the appended clalms.
''
Claims (28)
1. A thermoplastic resin blend comprising:
(a) a relatively low molecular weight polybutylene terephthalate resin;
(b) a relatively high molecular weight polyester resin; and (c) an effective melt viscosity stabilizing amount of (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl ox mixed phosphite having at least one hydrogen or alkyl group, or (iii) a Group IB or IIB metal phosphate salt, (iv) a phosphorous oxo acid or (v) a mixture of any of the foregoing.
(a) a relatively low molecular weight polybutylene terephthalate resin;
(b) a relatively high molecular weight polyester resin; and (c) an effective melt viscosity stabilizing amount of (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl ox mixed phosphite having at least one hydrogen or alkyl group, or (iii) a Group IB or IIB metal phosphate salt, (iv) a phosphorous oxo acid or (v) a mixture of any of the foregoing.
2. A thermoplastic resin blend as defined in Claim 1 wherein said component (a) has a melt viscosity of less than 600 poise.
3. A thermoplastic resin blend as defined in Claim 2 wherein said component (a) has a melt viscosity of less than about 450 poise.
4. A thermoplastic resin blend as defined in Claim 1 wherein said component (b) has a melt viscosity of greater than about 600 poise.
5. A thermoplastic resin blend as defined in Claim 1 wherein said component (b) has a melt viscosity of greater than about 900 poise.
6. A thermoplastic resin blend as defined in Claim 1 wherein said component (a) comprises a poly(1,4-butylene terephthalate) resin.
7. A thermoplastic resin blend as defined in Claim 1 wherein said component (b) comprises a poly(1,4-butylene terephthalate) resin.
8. A thermoplastic resin blend as defined in Claim 1 wherein said component (b) comprises polyethylene terephthalate, polycyclohexane dimethylene terephthalate or a mixture thereof.
9. A thermoplastic resin blend as defined in Claim 1 wherein said acidic phosphate salt component (c)(i) is selected from zinc monophosphate, monosodium phosphate, sodium acid pyrophosphate and mixtures of any of the foregoing.
10. A thermoplastic resin blend as defined in Claim 1 wherein said phosphite component (c)(ii) comprises a phosphite of the general formula P-(OR')3 wherein each R' is the same or different and independently represents hydrogen, alkyl, aryl or a mixture of alkyl and aryl provided that at least one R' group is hydrogen or alkyl.
11. A thermoplastic resin blend as defined in Claim 10 wherein said phosphite component (c)(ii) is selected from the group of diisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, phenyl iiisodecyl phosphite, ethyl hexyl diphenyl phosphite, stearyl phosphite and mixtures of any of the foregoing.
12. A thermoplastic resin blend as defined in Claim 11 wherein said phosphite component (c)(ii) comprises diphenylisodecyl phosphite.
13. A thermoplastic resin blend as defined in Claim 1 wherein said component (c)(iii) comprises zinc phosphate.
14. A thermoplastic resin blend as defined in Claim 1 wherein said phosphorous oxo acid (c)(iv) comprises phosphorous acid, phosphoric acid, polyphosphoric acid, hypophosphorous acid or mixtures thereof.
15. A thermoplastic resin blend as defined in Claim 1 comprising from about 30 to about 70 parts by weight component (a), from about 70 to about 30 parts by weight component (b), and from about 0.1 to about 10 parts by weight component (c) based on 100 total parts by weight of components (a), (b) and (c).
16. A thermoplastic resin blend as defined in Claim 1 further comprising (d) a thermoplastic resin selected from polycarbonates, polyester carbonates, polyarylates and mixtures of any of the foregoing.
17. A thermoplastic resin blend as defined in Claim 16 wherein said component (d) comprises a poly(bisphenol A)carbonate.
18. A thermoplastic resin blend as defined in Claim 1 further comprising (e) a reinforcing agent comprising glass fibers, talc, mica, clay or mixtures thereof.
19. A thermoplastic resin blend as defined in Claim 1 further comprising (f) a flame retardant agent.
20. A thermoplastic resin blend as defined in Claim 1 further comprising (g) an additive selected from impact modifiers, pigments, fillers, plasticizers, processing aids, UV stabilizers, antioxidants and mixtures of any of the foregoing.
21. An article prepared from a composition as defined in Claim 1.
22. A process for stabilizing the melt viscosity of a thermoplastic resin blend comprising a relatively low molecular weight PBT and a relatively high molecular weight polyester, said process comprising adding to said blend an effective amount of a phosphorus compound comprising (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl group, (iii) a Group IB or IIB metal phosphate salt, (iv) a phosphorous oxo acid or (v) a mixture of any of the foregoing.
23. A process as defined in Claim 22 wherein said relatively low molecular weight PBT resin has a melt viscosity of less than about 450 poise and said relatively high molecular weight polyester resin has a melt viscosity of greater than about 900 poise.
24. A process as defined in Claim 23 wherein said high molecular weight polyester resin comprises polybutylene terephthalate, polyethylene terephthalate, polycyclohexane dimethylene terepthalate, or a mixture of any of the foregoing.
25. A process as defined in Claim 22 wherein said phosphorus compound is selected from the group consisting of zinc phosphate, diphenylisodecyl phosphite, monosodium phosphate, sodium acid pyrophosphate and mixtures of any of the foregoing.
26. A thermoplastic resin blend as defined in Claim 25 wherein said phosphorus component comprises zinc phosphate.
27. A thermoplastic resin blend having improved melt viscosity stability consisting essentially of (a) a low molecular weight polybutylene terephthalate resin;
(b) a high molecular weight polyester resin;
and (c) an effective melt viscosity stabilizing amount of (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl group, (iii) a Group IB or IIB metal phosphate salt, (iv) a phosphorous oxo acid or (v) a mixture of any of the foregoing; and, optionally, one or more of the following components:
(d) a thermoplastic resin selected from polycarbonates, polyester carbonates, polyarylates and mixtures of any of the foregoing;
(e) a reinforcing agent;
(f) a flame retardant agent; and (g) an additive selected from impact modifiers, pigments, fillers, colorants, plasticizers, processing aids, UV stabilizers, antioxidants and mixtures of any of the foregoing.
(b) a high molecular weight polyester resin;
and (c) an effective melt viscosity stabilizing amount of (i) an acidic phosphate salt, (ii) an acid, alkyl, aryl or mixed phosphite having at least one hydrogen or alkyl group, (iii) a Group IB or IIB metal phosphate salt, (iv) a phosphorous oxo acid or (v) a mixture of any of the foregoing; and, optionally, one or more of the following components:
(d) a thermoplastic resin selected from polycarbonates, polyester carbonates, polyarylates and mixtures of any of the foregoing;
(e) a reinforcing agent;
(f) a flame retardant agent; and (g) an additive selected from impact modifiers, pigments, fillers, colorants, plasticizers, processing aids, UV stabilizers, antioxidants and mixtures of any of the foregoing.
28. The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99473892A | 1992-12-22 | 1992-12-22 | |
| US994,738 | 1992-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2103420A1 true CA2103420A1 (en) | 1994-06-23 |
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ID=25540998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002103420A Abandoned CA2103420A1 (en) | 1992-12-22 | 1993-11-18 | Stabilization of low molecular weight polybutylene terephthalate/polyester blends with phosphorus compounds |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5367011A (en) |
| EP (1) | EP0604074B1 (en) |
| JP (1) | JP2721479B2 (en) |
| CA (1) | CA2103420A1 (en) |
| DE (1) | DE69333179T2 (en) |
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-
1993
- 1993-11-18 CA CA002103420A patent/CA2103420A1/en not_active Abandoned
- 1993-12-08 US US08/164,642 patent/US5367011A/en not_active Expired - Lifetime
- 1993-12-10 EP EP93309946A patent/EP0604074B1/en not_active Expired - Lifetime
- 1993-12-10 DE DE69333179T patent/DE69333179T2/en not_active Expired - Lifetime
- 1993-12-21 JP JP5320732A patent/JP2721479B2/en not_active Expired - Fee Related
-
1994
- 1994-09-19 US US08/308,722 patent/US5589530A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2721479B2 (en) | 1998-03-04 |
| JPH06279664A (en) | 1994-10-04 |
| EP0604074A1 (en) | 1994-06-29 |
| EP0604074B1 (en) | 2003-09-03 |
| US5589530A (en) | 1996-12-31 |
| DE69333179D1 (en) | 2003-10-09 |
| DE69333179T2 (en) | 2004-04-15 |
| US5367011A (en) | 1994-11-22 |
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| EEER | Examination request | ||
| FZDE | Discontinued |