CA2039130A1 - Polyesters modified with abs terpolymers - Google Patents
Polyesters modified with abs terpolymersInfo
- Publication number
- CA2039130A1 CA2039130A1 CA 2039130 CA2039130A CA2039130A1 CA 2039130 A1 CA2039130 A1 CA 2039130A1 CA 2039130 CA2039130 CA 2039130 CA 2039130 A CA2039130 A CA 2039130A CA 2039130 A1 CA2039130 A1 CA 2039130A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition
- polyester resin
- parts
- abs
- 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
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 19
- 229920000728 polyester Polymers 0.000 title description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 23
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 23
- 229920001225 polyester resin Polymers 0.000 claims abstract description 21
- 239000004645 polyester resin Substances 0.000 claims abstract description 21
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract 3
- 239000011347 resin Substances 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 150000002531 isophthalic acids Chemical class 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SYJPAKDNFZLSMV-HYXAFXHYSA-N (Z)-2-methylpropanal oxime Chemical compound CC(C)\C=N/O SYJPAKDNFZLSMV-HYXAFXHYSA-N 0.000 description 1
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 1
- APTGHASZJUAUCP-UHFFFAOYSA-N 1-n,4-n-di(octan-2-yl)benzene-1,4-diamine Chemical compound CCCCCCC(C)NC1=CC=C(NC(C)CCCCCC)C=C1 APTGHASZJUAUCP-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- GZZLQUBMUXEOBE-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diol Chemical compound OCCC(C)CC(C)(C)CO GZZLQUBMUXEOBE-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- RBQLGIKHSXQZTB-UHFFFAOYSA-N 3-methylpentane-2,4-diol Chemical compound CC(O)C(C)C(C)O RBQLGIKHSXQZTB-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical group CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- UXCKXHXXSNDUMI-UHFFFAOYSA-L copper;2-carboxy-6-phenylphenolate Chemical compound [Cu+2].OC1=C(C([O-])=O)C=CC=C1C1=CC=CC=C1.OC1=C(C([O-])=O)C=CC=C1C1=CC=CC=C1 UXCKXHXXSNDUMI-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- RGCHNYAILFZUPL-UHFFFAOYSA-N trimethyl benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1 RGCHNYAILFZUPL-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
The impact strength of polyester resins, preferably polybutylene terephthalate resins can be improved by the addition of an ABS graft terpolymer wherein there is a specific weight ratio of the A/B/S
components in the terpolymer to each other.
The impact strength of polyester resins, preferably polybutylene terephthalate resins can be improved by the addition of an ABS graft terpolymer wherein there is a specific weight ratio of the A/B/S
components in the terpolymer to each other.
Description
POLYESTERS MODIFIED WITH ABS TE~POLYMERS
Omar M. Boutni Ping Y. Liu This invention relates to high-impact mixtures of polybutylene terephthalate and ABS-graft polymer having a defined ratio of the A/8/S components therein.
BACR~ROUND OF THE INVENTION
Polybutylene terephthalates have acquired consid-erable significance as thermoplastic molding compositions by virtue of their valuable technological properties, e.g., chemical resistance, rigidity, hardness, abrasion resistance, stability under dynamic and thermal stressing, and rapid processibility. A
disadvantage of these molding compositions is that their notched Izod impact strength is inadequate for certain specific applications. Proposals have been put forward for increasing the toughness of thermoplastic polyesters by the addition of co-condensation of other 2039~:~o polymers, particularly those based on modified elastomers and polyolefins (German Offenlegungsschrifts Nos. 1,694,173 and 1,928,369; German Auslegeschrifts Nos. 1,961,226 and 1,962,855; German Offenlegungsschrifts Nos. 2,248,242, 2,310,034, 2,357,406 and 2,364,318 and U.S.Pat. Nos. 3,236,914 and 3,723,574). However, the proposed measures are attended by the disadvantage that the improvement in toughness is accompanied by a significant deterioration in other properties.
DESCRIPTION OF THE INVENTION
It has now been discovered that compositions comprising of polyester resin and a ABS terpolymer will have improved impact strength as well as knit line strength when a terpolymer is used that has a specific weight ratio of the acrylonitrile-butadine--styrene components therein. Specifically, it has been discovered that the optimum weight ratio of said components, is (for every one hundred weight parts of ABS resin) from about 13 to about 18 parts by weight of - acrylonitrile, from about 45 to about 47 parts by weight of butadine, and from about 35 to about 42 parts by weigbt of styrene.
DETAILED DESCRIPTION OF THE INVENTION
The preferred polyesters utilized in the present invention are higher molecular weight polyesters, 2039~30 _3- 8CV-4701 most preferably linear polymeric glycol esters of terephthalic acid and isophthalic acids. They can be prepared by known techniques such as by the alcoholysis of esters of the phthalic acid with a glycol and subsequent polymerization, by heating glycols with the free acids or with halide derivatives thereof, and similar processes. These are described in U.S. Pat. Nos. 2,465,319 and 3,047,539, and elsewhere.
In addition to the phthalates, amounts~ e.g., from about 0.5 to 15% by weight, of other aromatic dicar-boxylic acids, such as naphthalene dicarboxylic acid, can be present in the polyester component. Although the term "linear" is used, the reactants can also include amounts of tri- or polyfunctional branching agents, such as trimethylolpropane, pentaerythritol, and trimethyl trimesate.
Preferred polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula:
O
C
_o-(cH2)n--c ~
Omar M. Boutni Ping Y. Liu This invention relates to high-impact mixtures of polybutylene terephthalate and ABS-graft polymer having a defined ratio of the A/8/S components therein.
BACR~ROUND OF THE INVENTION
Polybutylene terephthalates have acquired consid-erable significance as thermoplastic molding compositions by virtue of their valuable technological properties, e.g., chemical resistance, rigidity, hardness, abrasion resistance, stability under dynamic and thermal stressing, and rapid processibility. A
disadvantage of these molding compositions is that their notched Izod impact strength is inadequate for certain specific applications. Proposals have been put forward for increasing the toughness of thermoplastic polyesters by the addition of co-condensation of other 2039~:~o polymers, particularly those based on modified elastomers and polyolefins (German Offenlegungsschrifts Nos. 1,694,173 and 1,928,369; German Auslegeschrifts Nos. 1,961,226 and 1,962,855; German Offenlegungsschrifts Nos. 2,248,242, 2,310,034, 2,357,406 and 2,364,318 and U.S.Pat. Nos. 3,236,914 and 3,723,574). However, the proposed measures are attended by the disadvantage that the improvement in toughness is accompanied by a significant deterioration in other properties.
DESCRIPTION OF THE INVENTION
It has now been discovered that compositions comprising of polyester resin and a ABS terpolymer will have improved impact strength as well as knit line strength when a terpolymer is used that has a specific weight ratio of the acrylonitrile-butadine--styrene components therein. Specifically, it has been discovered that the optimum weight ratio of said components, is (for every one hundred weight parts of ABS resin) from about 13 to about 18 parts by weight of - acrylonitrile, from about 45 to about 47 parts by weight of butadine, and from about 35 to about 42 parts by weigbt of styrene.
DETAILED DESCRIPTION OF THE INVENTION
The preferred polyesters utilized in the present invention are higher molecular weight polyesters, 2039~30 _3- 8CV-4701 most preferably linear polymeric glycol esters of terephthalic acid and isophthalic acids. They can be prepared by known techniques such as by the alcoholysis of esters of the phthalic acid with a glycol and subsequent polymerization, by heating glycols with the free acids or with halide derivatives thereof, and similar processes. These are described in U.S. Pat. Nos. 2,465,319 and 3,047,539, and elsewhere.
In addition to the phthalates, amounts~ e.g., from about 0.5 to 15% by weight, of other aromatic dicar-boxylic acids, such as naphthalene dicarboxylic acid, can be present in the polyester component. Although the term "linear" is used, the reactants can also include amounts of tri- or polyfunctional branching agents, such as trimethylolpropane, pentaerythritol, and trimethyl trimesate.
Preferred polyesters will be of the family consisting of high molecular weight, polymeric glycol terephthalates or isophthalates having repeating units of the general formula:
O
C
_o-(cH2)n--c ~
wherein n is a whole number of from 2 to 10, pre-ferably from 2 to 4, and mixtures of such esters, including copolyesters of terephthalic and isophthalic acids of up to about 30 mole % isophthalic units.
Especially preferred polyesters are poly(ethylene terephthalate and poly(butylene terephthalate). The most preferred polyesters are poly(butylene terephthalates), with poly(l,4-butylene terephthalate being especially preferred.
The preferred polybutyLene terephthalates contain at least 90 mole percent, based on the dicarboxylic acid component of terephthalic acid residues and at least 90 mole percent, based on the diol component, of 1,4-butane diol residues.
In addition to terephthalic acid residues, the preferred polybutylene terephthalates may contain up to 10 mole percent of residues of other aromatic, aliphatic or cycloaliphatic dicarboxylic acids, for example, succinic acid, adipic acid or isophthalic acid residues. In addition to butane diol residues, they may contain up to 10 mole percent of residues of another diol which may correspond to the following formula:
HO-CnH2n-OH
in which n is an integer of from 2 to 10. More 3~
Especially preferred polyesters are poly(ethylene terephthalate and poly(butylene terephthalate). The most preferred polyesters are poly(butylene terephthalates), with poly(l,4-butylene terephthalate being especially preferred.
The preferred polybutyLene terephthalates contain at least 90 mole percent, based on the dicarboxylic acid component of terephthalic acid residues and at least 90 mole percent, based on the diol component, of 1,4-butane diol residues.
In addition to terephthalic acid residues, the preferred polybutylene terephthalates may contain up to 10 mole percent of residues of other aromatic, aliphatic or cycloaliphatic dicarboxylic acids, for example, succinic acid, adipic acid or isophthalic acid residues. In addition to butane diol residues, they may contain up to 10 mole percent of residues of another diol which may correspond to the following formula:
HO-CnH2n-OH
in which n is an integer of from 2 to 10. More 3~
particularly, up to 10 mole percent of alkyl-substituted diols, such as neopen~yl glycol, 2,2,4-trimethyl-1, 6-hexane diol, 2-ethyl-1.3-propane diol, 2,2,4-trimethyl-1.3-pentane diol, 2-methyl-2,4-pentane diol, 3-methyl-2.4-pentane diol or 2-ethyl-1,3-hexane diol may also be incorporated ~German Offenlegungsschrifts Nos. 2,407,674; 2,407,776 and 2,715,932).
The preferred polybutylene terephthalates may aLso be branched by compounds having a branching effect, such as polycarboxylic acids or polyols (German Auslegeschrift No. 1,900,270).
The most preferred polybutylene terephthalates have an intrinsic viscosity of generally from 0.7 to 1.5 dl/g, preferably from 0.8 to 1.3 dl/g and, more particularly, from 0.8 to 1.05 dl/g, as measured in phenol/o-dichlorobenzene (1:1 parts by weight).
It has now been discovered that mixtures of a polyester resin or resins and a ABS terpolymer will have improved impact strength, over previous polyester-ABS mixtures, when a terpolymer is used that has a specific weight ratio of the acrylonitrile~butadine-styrene components therein.
Specifically, it has been discovered that the optimum weight ratio of said components, is, for every one hundred weight parts of ABS resin, from about 13 to ;~039130 about 18 parts by weight of acrylonitrile, from about 45 to about 47 parts by weight of butadiene, and from about 35 to about 42 parts by weight of styrene.
The processes for producing ABS terpolymers are well known in the art. Suitable ABS terpolymers for use in the present invention are also available commercially.
The compositions of the present invention will preferably contain (a) from about 40 % to about 98 %
by weight, and most preferably from about 60% to about 97% by weight, of at least one polyester preferably selected from the group consisting of poly(ethylene terephthalate) and a poly(butylene terephthalate), each polyester comprising 0-100% of the polyester component, and, most preferably a poly(butylene terephthalate) polyester; and (b) from about 2 % to about 60 %
by weight, and most preferably from about 3% to about 40% by weight, of the specified ABS ter-polymer, said weight percentages being based on the total weight of the polyester resins and the ABS
terpolymer.
It should be understood that the compositions obtained according to this invention may contain one or more conventional additives such as, for example, antioxidants, carbon black, reinforcing agents, plasticizers, lubricity promoters, color stabilizers, 20:~9~30 ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers, mold release agents and the like.
Satisfactory thermal, oxidative and/or ultraviolet stabilizers comprise phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amine groups, hydroxyazines, oximes, polymeric phenolic esters and salts of multivalent metals in which the metal is in its lower state.
Representative phenol derivatives useful as stabilizers include 3,5-di-tert-butyl-hydroxy hydro-cinnamic triester with 1,3, 5-tris-(2-hydroxyethyl-s--triazine-2,4,6-(lH, 3H, 5H) trione; 4,4'-bis--(2,6-ditertiary-butylphenol); 1,3,5-trimethyl-2,4,6--tris-(3,5-ditertiary-butyl-4-hydroxylbenzyl)benzene and 4,4'-butylidene-bis (6-tertiary-butyl-m-cresol).
Various inorganic metal salts or hydroxides can be used as well as organic complexes such as nickel dibutyl dithiocarbamate, manganous salicylate and copper 3-phenylsalicylate. Typical amine stabilizers include N,N'-bis(betanaphthyl)-p-phenylenediamine; N,N'-bis-(l-methylheptyl)-p-phenylenediamine and either phenyl--beta-napththyl amine or its reaction products with aldehydes. Mixtures of hindered phenols with esters or thiodipropionic, mercaptides and phosphite esters are particularly useful. Additional stabilization to ultraviolet light can be obtained by compounding with ~ O~ 9 ~3 O
The preferred polybutylene terephthalates may aLso be branched by compounds having a branching effect, such as polycarboxylic acids or polyols (German Auslegeschrift No. 1,900,270).
The most preferred polybutylene terephthalates have an intrinsic viscosity of generally from 0.7 to 1.5 dl/g, preferably from 0.8 to 1.3 dl/g and, more particularly, from 0.8 to 1.05 dl/g, as measured in phenol/o-dichlorobenzene (1:1 parts by weight).
It has now been discovered that mixtures of a polyester resin or resins and a ABS terpolymer will have improved impact strength, over previous polyester-ABS mixtures, when a terpolymer is used that has a specific weight ratio of the acrylonitrile~butadine-styrene components therein.
Specifically, it has been discovered that the optimum weight ratio of said components, is, for every one hundred weight parts of ABS resin, from about 13 to ;~039130 about 18 parts by weight of acrylonitrile, from about 45 to about 47 parts by weight of butadiene, and from about 35 to about 42 parts by weight of styrene.
The processes for producing ABS terpolymers are well known in the art. Suitable ABS terpolymers for use in the present invention are also available commercially.
The compositions of the present invention will preferably contain (a) from about 40 % to about 98 %
by weight, and most preferably from about 60% to about 97% by weight, of at least one polyester preferably selected from the group consisting of poly(ethylene terephthalate) and a poly(butylene terephthalate), each polyester comprising 0-100% of the polyester component, and, most preferably a poly(butylene terephthalate) polyester; and (b) from about 2 % to about 60 %
by weight, and most preferably from about 3% to about 40% by weight, of the specified ABS ter-polymer, said weight percentages being based on the total weight of the polyester resins and the ABS
terpolymer.
It should be understood that the compositions obtained according to this invention may contain one or more conventional additives such as, for example, antioxidants, carbon black, reinforcing agents, plasticizers, lubricity promoters, color stabilizers, 20:~9~30 ultraviolet absorbers, X-ray opacifiers, dyes, pigments, fillers, mold release agents and the like.
Satisfactory thermal, oxidative and/or ultraviolet stabilizers comprise phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amine groups, hydroxyazines, oximes, polymeric phenolic esters and salts of multivalent metals in which the metal is in its lower state.
Representative phenol derivatives useful as stabilizers include 3,5-di-tert-butyl-hydroxy hydro-cinnamic triester with 1,3, 5-tris-(2-hydroxyethyl-s--triazine-2,4,6-(lH, 3H, 5H) trione; 4,4'-bis--(2,6-ditertiary-butylphenol); 1,3,5-trimethyl-2,4,6--tris-(3,5-ditertiary-butyl-4-hydroxylbenzyl)benzene and 4,4'-butylidene-bis (6-tertiary-butyl-m-cresol).
Various inorganic metal salts or hydroxides can be used as well as organic complexes such as nickel dibutyl dithiocarbamate, manganous salicylate and copper 3-phenylsalicylate. Typical amine stabilizers include N,N'-bis(betanaphthyl)-p-phenylenediamine; N,N'-bis-(l-methylheptyl)-p-phenylenediamine and either phenyl--beta-napththyl amine or its reaction products with aldehydes. Mixtures of hindered phenols with esters or thiodipropionic, mercaptides and phosphite esters are particularly useful. Additional stabilization to ultraviolet light can be obtained by compounding with ~ O~ 9 ~3 O
various UV absorbers such as substituted benzophenones and/or benzotriazoles.
Particularly useful stabilizers are hindered phenols which include phenols of the formula ~ R
wherein Rl and R3 are hydrocarbon groups having from one to about 20 carbon atoms, and R2 is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, and bisphenol of the formula O A ~ (C~2)n ~ A
wherein R4, Rs and R6 are each a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, one of the two A's on each ring is a hydroxyl group and the other A on each ring is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms; and n is an integer of from 0 to about 20.
Preferred hindered phenols useful in this invention include 2,6-di-tert-butyl-4-methyl-phenol, commonly known as BHT (sold under the tradename Ionol by Shell Chemical Co.); 4,4-methylene bis(2,6-di-tert--butylphenol) and 2,6-di-tert-butyl-4-n-butylphenol Z O ~ ~ ~3 _9_ 8CV-4701 (sold under the tradename Ethyl 702 and Ethyl 744, respectively, by Ethyl Corp.); and tetrakis[methylene 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) proprionate]-methane and stearyl-3-(3',5'-di-tertbutyl-4'-hydroxy-phenyl) proprionate (sold under the tradenames Irganox1010 and Irganox 1076, respectively, by Ciba-Geigy).
The composition of the present invention will preferably include reinforcing agents such as fibrous (filamentous) glass and/or fillers, such as mineral fillers such as clay, talc and the like, preferably mica. The fillers can be untreated or treated with silane or titanate coupling agents, etc.
The preferred reinforcing agent for use in the present invention is filamentous glass, which is is well known in the art.
The components of the composition of the present invention can be intimately blended in a number of procedures. In one way, the various additives to the polyester resin(s) are put into an extrusion compounder with the dry polyester resin(s) and the blend is heated at an elevated temperature, e.g., 450-550F., and extruded to produce molding pellets.
In another procedure, the additives are mixed with the polyester resin(s) by blending at ordinary temperatures, then the blend is fluxed on a mill, heated, e.g., at 450-550F., then cooled and comminuted; or the blend can be extruded at 450-550F., cooled and chopped. The additives are mixed with the powdered or granular polyester(s) and the mixture can be heated and directly formed into blow molded items using machines which compound and mold.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples are presented to more fully and clearly illustrate the present invention.
They are presented as illustrative of the invention and are not to be construed as limiting the invention thereto. In the examples all parts and percentages are on a weight basis unless otherwise specified.
In all the examples, the compositions were pre-pared by melt blending the polyester resins and the indicated additional components as set forth in the Tables below using a Prodex single screw extruder at approximately 470F. The resulting polymeric composition was formed, by injection molding, into test specimens, the size of which was consistent which what is specified in the ASTM methods set forth below.
Certain properties of the composition were tested with the results of these tests also set forth in the Tables below.
The following ASTM methods were used in determining the physical characteristics of the com-positions:
;~039~3S3 ~ 8CV-4701 Double Gate Unnotched Izod ASTM D256 Notched Izod ASTM D256 Example l illustrates an ABS composition having proportions of the relative components therein which is outside the scope of the present invention and is presented for illustrat;ve purposes only. Examples 2 to 7 clearly demonstrate that the claimed composition range of A/B/S is critical to upgrade the NI properties as well as the DG,UNI properties of polyester/ABS
blends.
~ ~ 39 ~3~.~
TABLE I
EX. 1 EX. 2 EX. 2 EX. 4 PBT%91.8 95.8 91.8 91.8 ABS%8.0 4.0 8.0 8.0 A/B/S (16/38/46) (13/46/41) (13/46/41) (15145140) STAB 0~2 0.2 0.2 0.2 DTUL,F,@264 154 138 145 154 psi NI 1.55 1.65 1.81 1.55 UNI, DG0.98 1.42 1.82 1.55 TABLE II
PBT~/~*~91.8 84.8 79.8 ABS% 8.0 15.0 20.0 A/B/S (18/47/35) (13/46/41) (13/46/41) STAB 0.2 0.2 0.2 DTUL,F,@264psi 158 162 168 NI 1.87 1.88 2.61 UNI, DG 1.33 1.49 1.71 The stabilizer (STAB) utilized was Irganox 1076.
PBT is poly(l,4-butylene terephthalate), Valox~ 315 from the General Electric Company.
Particularly useful stabilizers are hindered phenols which include phenols of the formula ~ R
wherein Rl and R3 are hydrocarbon groups having from one to about 20 carbon atoms, and R2 is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, and bisphenol of the formula O A ~ (C~2)n ~ A
wherein R4, Rs and R6 are each a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms, one of the two A's on each ring is a hydroxyl group and the other A on each ring is a hydrogen atom or a hydrocarbon group having from one to about 20 carbon atoms; and n is an integer of from 0 to about 20.
Preferred hindered phenols useful in this invention include 2,6-di-tert-butyl-4-methyl-phenol, commonly known as BHT (sold under the tradename Ionol by Shell Chemical Co.); 4,4-methylene bis(2,6-di-tert--butylphenol) and 2,6-di-tert-butyl-4-n-butylphenol Z O ~ ~ ~3 _9_ 8CV-4701 (sold under the tradename Ethyl 702 and Ethyl 744, respectively, by Ethyl Corp.); and tetrakis[methylene 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) proprionate]-methane and stearyl-3-(3',5'-di-tertbutyl-4'-hydroxy-phenyl) proprionate (sold under the tradenames Irganox1010 and Irganox 1076, respectively, by Ciba-Geigy).
The composition of the present invention will preferably include reinforcing agents such as fibrous (filamentous) glass and/or fillers, such as mineral fillers such as clay, talc and the like, preferably mica. The fillers can be untreated or treated with silane or titanate coupling agents, etc.
The preferred reinforcing agent for use in the present invention is filamentous glass, which is is well known in the art.
The components of the composition of the present invention can be intimately blended in a number of procedures. In one way, the various additives to the polyester resin(s) are put into an extrusion compounder with the dry polyester resin(s) and the blend is heated at an elevated temperature, e.g., 450-550F., and extruded to produce molding pellets.
In another procedure, the additives are mixed with the polyester resin(s) by blending at ordinary temperatures, then the blend is fluxed on a mill, heated, e.g., at 450-550F., then cooled and comminuted; or the blend can be extruded at 450-550F., cooled and chopped. The additives are mixed with the powdered or granular polyester(s) and the mixture can be heated and directly formed into blow molded items using machines which compound and mold.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples are presented to more fully and clearly illustrate the present invention.
They are presented as illustrative of the invention and are not to be construed as limiting the invention thereto. In the examples all parts and percentages are on a weight basis unless otherwise specified.
In all the examples, the compositions were pre-pared by melt blending the polyester resins and the indicated additional components as set forth in the Tables below using a Prodex single screw extruder at approximately 470F. The resulting polymeric composition was formed, by injection molding, into test specimens, the size of which was consistent which what is specified in the ASTM methods set forth below.
Certain properties of the composition were tested with the results of these tests also set forth in the Tables below.
The following ASTM methods were used in determining the physical characteristics of the com-positions:
;~039~3S3 ~ 8CV-4701 Double Gate Unnotched Izod ASTM D256 Notched Izod ASTM D256 Example l illustrates an ABS composition having proportions of the relative components therein which is outside the scope of the present invention and is presented for illustrat;ve purposes only. Examples 2 to 7 clearly demonstrate that the claimed composition range of A/B/S is critical to upgrade the NI properties as well as the DG,UNI properties of polyester/ABS
blends.
~ ~ 39 ~3~.~
TABLE I
EX. 1 EX. 2 EX. 2 EX. 4 PBT%91.8 95.8 91.8 91.8 ABS%8.0 4.0 8.0 8.0 A/B/S (16/38/46) (13/46/41) (13/46/41) (15145140) STAB 0~2 0.2 0.2 0.2 DTUL,F,@264 154 138 145 154 psi NI 1.55 1.65 1.81 1.55 UNI, DG0.98 1.42 1.82 1.55 TABLE II
PBT~/~*~91.8 84.8 79.8 ABS% 8.0 15.0 20.0 A/B/S (18/47/35) (13/46/41) (13/46/41) STAB 0.2 0.2 0.2 DTUL,F,@264psi 158 162 168 NI 1.87 1.88 2.61 UNI, DG 1.33 1.49 1.71 The stabilizer (STAB) utilized was Irganox 1076.
PBT is poly(l,4-butylene terephthalate), Valox~ 315 from the General Electric Company.
Claims (14)
1. A thermoplastic composition comprising (a) at least one polyester resin; and (b) an ABS terpolymer resin, characterized by, in the ABS terpolymer, the weight ratio of the A component ranges from about 13 to about 18 parts by weight; the weight ratio of the B
component ranges from about 45 to about 47 parts by weight; and the weight ratio of the S component ranges from about 35 to about 42 parts by weight, based on the total weight of the ABS terpolymer.
component ranges from about 45 to about 47 parts by weight; and the weight ratio of the S component ranges from about 35 to about 42 parts by weight, based on the total weight of the ABS terpolymer.
2. The composition of claim 1 wherein the amount of polyester resin ranges from about 40 to about 98 parts by weight per one hundred parts by weight of the total of the polyester resin and the ABS terpolymer.
3. The composition of claim 2 wherein the amount of polyester resin ranges from about 60 to about 97 parts by weight per one hundred parts by weight of the total of the polyester resin and the ABS terpolymer.
4. The composition of Claim 1 wherein the at least one polyester resin is a high molecular weight linear thermoplastic polyester resin selected from the group consisting of polymeric glycol terephthalate and isophthalate esters having repeating units of the general formula:
wherein n is a whole number of from 2 to 10, or a mixture of such esters.
wherein n is a whole number of from 2 to 10, or a mixture of such esters.
5. The composition as defined in claim 4 wherein the polyester resin is a poly (butylene terephthalate) ester.
6. The composition as defined in claim 5 wherein the polyester resin is poly(l,4-butylene terephthalate).
7. The composition as defined in claim 3 wherein the polyester resin is poly(ethylene terephthalate) ester.
8. The composition of claim 4 wherein the at least one polyester resin is a mixture of poly(l,4-butylene terephthalate) and poly(ethylene terephthalate) ester resins.
9. The composition of claim 1 wherein the amount of ABS terpolymer ranges from about 2 to about 60 parts by weight per one hundred parts by weight of the total of the polyester resin and the ABS terpolymer.
10. The composition of claim 9 wherein the amount of ABS terpolymer ranges from about 3 to about 40 parts by weight per one hundred parts by weight of the total of the polyester resin and the ABS terpolymer.
11. The composition of claim 1 which further contains an effective stabilizing amount of at least one thermal stabilizer.
12. The composition of claim 1 which further contains a filler.
13. The composition of claim 1 which further contains an effective reinforcing amount of at least one reinforcing agent.
14. The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2039130 CA2039130A1 (en) | 1991-01-10 | 1991-01-10 | Polyesters modified with abs terpolymers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2039130 CA2039130A1 (en) | 1991-01-10 | 1991-01-10 | Polyesters modified with abs terpolymers |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2039130A1 true CA2039130A1 (en) | 1992-07-11 |
Family
ID=4147272
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2039130 Abandoned CA2039130A1 (en) | 1991-01-10 | 1991-01-10 | Polyesters modified with abs terpolymers |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA2039130A1 (en) |
-
1991
- 1991-01-10 CA CA 2039130 patent/CA2039130A1/en not_active Abandoned
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