CN1220287A - 相容化聚苯醚-聚酰胺树脂共混物抗冲改性组合物 - Google Patents
相容化聚苯醚-聚酰胺树脂共混物抗冲改性组合物 Download PDFInfo
- Publication number
- CN1220287A CN1220287A CN98122527A CN98122527A CN1220287A CN 1220287 A CN1220287 A CN 1220287A CN 98122527 A CN98122527 A CN 98122527A CN 98122527 A CN98122527 A CN 98122527A CN 1220287 A CN1220287 A CN 1220287A
- Authority
- CN
- China
- Prior art keywords
- composition
- acid
- methyl
- weight
- alkene
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- -1 polyphenylene Polymers 0.000 title claims abstract description 28
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 17
- 229920000265 Polyparaphenylene Polymers 0.000 title abstract 2
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 150000002905 orthoesters Chemical class 0.000 claims abstract description 10
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 19
- 229920000800 acrylic rubber Polymers 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000004609 Impact Modifier Substances 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 description 20
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 15
- 230000035939 shock Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920003656 Daiamid® Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004129 EU approved improving agent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 150000000344 2,6-naphthoquinones Chemical class 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WSUBIRCPENZBDS-UHFFFAOYSA-N 2-carbonochloridoylpentanedioic acid Chemical compound OC(=O)CCC(C(O)=O)C(Cl)=O WSUBIRCPENZBDS-UHFFFAOYSA-N 0.000 description 1
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-UHFFFAOYSA-N 0.000 description 1
- WKGCZVNVRCDJPF-UHFFFAOYSA-N 2-cyclohexylethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC1CCCCC1 WKGCZVNVRCDJPF-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- HZLCGUXUOFWCCN-UHFFFAOYSA-N 2-hydroxynonadecane-1,2,3-tricarboxylic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)(C(O)=O)CC(O)=O HZLCGUXUOFWCCN-UHFFFAOYSA-N 0.000 description 1
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 description 1
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- PLUZWNCOPUPWBY-UHFFFAOYSA-N CC(C(CCC(O)=O)(C(O)=O)Cl)=O Chemical compound CC(C(CCC(O)=O)(C(O)=O)Cl)=O PLUZWNCOPUPWBY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910014571 C—O—Si Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- GZZPOFFXKUVNSW-UHFFFAOYSA-N Dodecenoic acid Natural products OC(=O)CCCCCCCCCC=C GZZPOFFXKUVNSW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- BGRDGMRNKXEXQD-UHFFFAOYSA-N Maleic hydrazide Chemical compound OC1=CC=C(O)N=N1 BGRDGMRNKXEXQD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000393 Nylon 6/6T Polymers 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OLOZVPHKXALCRI-UHFFFAOYSA-L calcium malate Chemical compound [Ca+2].[O-]C(=O)C(O)CC([O-])=O OLOZVPHKXALCRI-UHFFFAOYSA-L 0.000 description 1
- 239000001362 calcium malate Substances 0.000 description 1
- 229940016114 calcium malate Drugs 0.000 description 1
- 235000011038 calcium malates Nutrition 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002092 orthoester group Chemical group 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 description 1
- 239000001415 potassium malate Substances 0.000 description 1
- 235000011033 potassium malate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
Abstract
本发明涉及包含以抗冲击性改进剂改性的相容化聚苯醚-聚酰胺树脂共混物的热塑性组合物,该改进剂包含至少两种能与聚酰胺树脂反应的部分。优选的抗冲击性改进剂是一种链烯(甲基)丙烯酸烷基酯共聚物,它包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的部分。本发明的组合物在物理性能上有所改善,特别是低温下测定的断裂能及形变。
Description
本发明涉及一种以抗冲击性改进剂(impact modifier)改性的相容化聚苯醚-聚酰胺树脂共混物热塑性组合物,该改进剂包含至少两种能与聚酰胺树脂反应的部分。
本发明还涉及用本发明组合物制成的制品。
聚(亚苯基醚)树脂(以下称“PPE”),由于具有在物理、化学及电气等方面独特的综合性能,因而是一种颇具商业价值的材料。而将这类树脂与聚酰胺树脂配混,制成相容化共混物,则可使综合性能进一步改善,例如具有耐化学性、高强度及高流动性。这种相容化共混物的例子可见诸于美国专利4,315,086(Ueno等人)、4,659,760(van der Meer)以及4,732,938(Grant等人)。这些共混物的性能可通过加入各种添加剂,例如抗冲击性改进剂、阻燃剂、光稳定剂、加工稳定剂、热稳定剂、抗氧剂及填料等,得到进一步提高。
PPE/聚酰胺共混物的物理性能受到汽车市场上各种最终用途制品的青睐,尤其是底罩以及各种外部零部件。许多这类零部件要经受诸如冲击之类各种意外的考验,因而要求有优异的耐冲击和韧性。同样是这些制品,由于要使用在世界的各个角落,遇到各种极端的温度,因而在最终用户的使用中还要经受大幅度温度差异的考验。因此,存在着对一种耐冲击和韧性在大温度范围内,尤其在低温下均有所改善的相容化PPE-聚酰胺组合物的需要。
上面所讨论的需求,已由于一种改良热塑性组合物的发现而得到全面的满足,该组合物包含:
(a)一种相容化聚苯醚-聚酰胺树脂共混物,以及
(b)一种链烯-(甲基)丙烯酸烷基酯共聚物,它包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯基团的部分。
下面,进一步详述本发明。
聚苯醚树脂是一类熟知的化合物,有时亦称之为聚苯氧树脂。合适的PPE及其制法的例子可见诸于美国专利3,306,874、3,306,875、3,257,357以及3,257,358。本发明的组合物将涵盖均聚物、共聚物以及经酚类化合物的氧化偶联反应获得的接枝共聚物。在本发明组合物中作为基础树脂使用的优选PPE由自2,6-二甲基苯酚衍生而来的PPE构成。还可以想到的是自2,6-二甲基苯酚与2,3,6-三甲基苯酚衍生而来的PPE共聚物。
尤其有用的PPE是聚(2,6-二甲基-1,4-亚苯基醚),其特性粘度(I.V.),按在25℃甲苯中浓度为每100毫升0.6克的溶液测定,为约0.30~约0.60dl/g。
可用于实施本发明的聚酰胺树脂是同属一类并被称作尼龙的树脂,其特征是包含酰胺基团(-C(O)NH-)。尼龙-6和尼龙-6,6是通常优选的聚酰胺,可经多种商业来源获得。然而,其他聚酰胺,例如尼龙-4,6、尼龙-12、尼龙-6,10、尼龙-6,9、尼龙6/6T以及尼龙6,6/6T,其中三胺含量低于约0.5%(重量)者,乃至其他的,例如无定形尼龙等也都可用于特定的PPE-聚酰胺用途。还可以使用各种聚酰胺的混合物以及聚酰胺的各种共聚物。用于本发明共混物的最优选聚酰胺是聚酰胺6,6。
聚酰胺可通过多种熟知的方法获得,例如可参见美国专利2,071,250、2,071,251、2,130,523、2,130,948、2,241,322、2,312,966以及2,512,606。举例说,尼龙-6是己内酰胺的聚合产物。尼龙-6,6是己二酸与1,6-二氨基己烷的缩合产物。类似地,尼龙-4,6是己二酸与1,4-二氨基丁烷的缩合产物。除己二酸之外,其他可用于制备尼龙的二酸包括壬二酸、癸二酸、十二碳二酸以及对苯二甲酸及间苯二甲酸。其他可使用的二胺包括间二甲苯二胺、二(4-氨基苯基)甲烷、二-(4-氨基环己基)甲烷、2,2-二-(4-氨基苯基)丙烷以及2,2-二-(4-氨基环己基)丙烷。己内酰胺与多种二酸及二胺的共聚物也可使用。
根据ISO307用0.5%(重量)在96%(重量)硫酸中的溶液测定,粘度值为约90~约350ml/g,优选为约110~约240ml/g的聚酰胺是优选使用的。
在制备组合物的过程中应在本发明共混物中使用相容剂。使用相容剂的双重目的在于,全面改善PPE-聚酰胺树脂共混物的物理性能,以及使得允许使用较大比例的聚酰胺组分。本文中所使用的术语“相容剂”是指能与PPE及聚酰胺树脂中二者之一或二者同时相互作用的多官能化合物。这种相互作用是化学的(如接枝)或物理的(如影响分散相的表面特性)。在任何一种情况下,所得到的PPE-聚酰胺组合物似乎都表现出相容性的改善,尤其体现在冲击强度、模具汇合线强度和/或伸长等方面的改善。本文所使用的术语“相容化聚苯醚-聚酰胺基础树脂”是指,那些在上面所讨论的试剂的作用下物理或化学地变得相容的组合物,以及那些不使用此类试剂已是物理相容的组合物,可详见美国专利3,379,792。
可在本发明的实施中使用的各种相容剂的例子包括:a)液态二烯聚合物、b)环氧化合物、c)氧化聚烯烃蜡、d)醌、e)有机硅烷化合物、f)多官能化合物及官能化PPE,如同下文所述,后者是用一种或多种前面提到的相容剂与PPE起反应获得的。
适合本发明使用的液态二烯聚合物(a)包括共轭二烯与至少一种选自其他共轭二烯、诸如苯乙烯和α-甲基苯乙烯的乙烯基单体、诸如乙烯、丙烯、丁烯-1、异丁烯、己烯-1、辛烯-1及十二碳烯-1之类烯烃的其他单体之间的均聚物及其混合物,其数均分子量为150~10,000,优选为150~5,000。这些均聚物和共聚物可采用例如美国专利4,054,612、3,876,721及3,428,699中所描述的方法制备,其中尤其包括聚丁二烯、聚异戊二烯、聚(1,3-戊二烯)、聚(丁二烯-异戊二烯)、聚(苯乙烯-丁二烯)、氯丁橡胶、聚(丁二烯-α-甲基苯乙烯)、聚(丁二烯-苯乙烯-异戊二烯)、聚(丁烯-丁二烯)等。
适合用于实施本发明的环氧化合物(b)包括:(1)通过多羟基苯酚(如双酚A、四溴双酚A、间苯二酚及氢醌)与表氯醇的缩合生成的环氧树脂;(2)通过多元醇(如乙二醇、丙二醇、丁二醇、聚乙二醇、聚丙二醇、季戊四醇及三羟甲基乙烷等)与表氯醇缩合生成的环氧树脂;(3)一元醇及单羟基苯酚的缩水甘油醚化产物,包括苯基缩水甘油基醚、丁基缩水甘油基醚及甲苯基缩水甘油基醚;(4)氨基化合物的缩水甘油基衍生物,例如苯胺的二缩水甘油基衍生物;以及(5)高级烯烃或环状烯烃或天然不饱和油类(如豆油)以及前面提到的液态二烯聚合物的环氧化产物。
氧化聚烯烃蜡(c)是熟知的,有关它的描述及其制法可见诸于美国专利3,822,227及3,756,999。一般而言,这类化合物是通过聚烯烃的氧化或悬浮氧化制备的。尤其优选的聚烯烃蜡是“HoechstWachs”。
适用于本发明的醌类化合物的特征是,在其未取代的衍生物分子中具有:至少一个六碳环;在该环的结构中至少有两个羰基,其中的两个羰基可位于同一环上,或者,若有一个以上的环,可在不同环上,只要其占据的位置对应于单环醌的1,2-或1,4-位即可;以及在环状结构中有至少两个碳-碳双键,且该环状结构上的所述碳-碳双键及羰基的碳-氧双键位于彼此共轭的位置。在未取代醌中有一个以上环的情况下,这些环可以是稠合的、非稠合的或二者兼而有之;非稠合环可以直接与一个直接碳-碳双键键合或与一个包含诸如-C=C-C=C-的共轭不饱和部分的烃基相键合。
取代的醌也属于本发明的范畴。在希望使用取代醌的情况下,取代度可以是1~“可取代氢原子的最大数目”。可存在于本发明取代醌结构中的各种取代基的例子包括卤素(如氯、溴、氟等);烃基,包括支链或非支链的、饱和及不饱和的烷基、芳基、烷芳基和环烷基及其卤代衍生物;以及其中含有杂原子,特别是氧、硫或磷的类似烃基,而且这些杂原子将取代基与醌环连接起来(例如氧键)。
可举出的各种醌的例子有:1,2-及1,4-苯并醌;2,6-二苯基醌;四甲基二醌、2,2’-及4,4’-二苯酚合苯醌;1,2-、1,4-及2,6-萘醌;氯醌;2-氯-1,4-苯并醌;2,6-二甲基苯并醌等。
适合作为相容剂的有机硅烷化合物(e)的特征是在分子中包含:(a)至少一个通过氧键与碳原子相连的硅原子以及(b)至少一个碳-碳双键或碳-碳三键和/或选自胺基或巯基的官能团,条件是该官能团不直接与该硅原子键合。
在此类化合物中,C-O-Si部分通常以烷氧基或酰氧基形式存在并直接与硅原子键合,其中烷氧基或酰氧基通常包含少于15个碳原子,还可以包含杂原子(如氧)。另外,在该化合物中还可以有一个以上的硅原子,如果有多个硅原子,则它们是通过氧键(如硅氧烷)、硅键或双官能有机基团(例如亚甲基或亚苯基)连接的。
合适的有机硅烷化合物的例子包括:γ氨基丙基三乙氧基硅烷、2-(3-环己基)乙基三甲氧基硅烷;1,3-二乙烯基四乙氧基硅烷;乙烯基三-(2-甲氧基乙氧基)硅烷;5-二环庚烯基三乙氧基硅烷及γ巯基丙基三甲氧基硅烷。
可在本发明实施中作为相容剂使用的多官能化合物(f)有3种类型。第一类多官能化合物是那些在分子中既有(a)碳-碳双键或碳-碳三键,又有(b)至少一个羧酸、酸酐、酰胺、酯、酰亚胺、氨基、环氧、原酸酯或羟基的多官能化合物。此类多官能化合物的例子包括马来酸;马来酐;富马酸;丙烯酸缩水甘油酯、衣康酸、乌头酸、马来酰亚胺;马来酰肼;由一种二胺与马来酐、马来酸、富马酸等反应生成的产物;二氯马来酐;马来酸酰胺;不饱和二羧酸(例如丙烯酸、丁烯酸、甲基丙烯酸、t-(端)乙基丙烯酸、戊烯酸);癸烯酸、十一碳烯酸、十二碳烯酸、亚油酸等);上述不饱和羧酸的酯、酸酰胺或酐;不饱和醇(例如烷基醇、巴豆醇、甲基乙烯基甲醇、4-戊烯-1-醇、1,4-己二烯-3-醇、3-丁烯-1,4-二醇、2,5-二甲基-3-己烯-2,5-二醇以及通式为CnH2n-5OH、CnH2n-7OH以及CnH2n-9OH的醇,其中n是最大为30的正整数);用-NH2基取代上述不饱和醇的-OH基所生成的不饱和胺;以及官能化的二烯聚合物及共聚物。其中,两个为本发明组合物所优选的相容剂是马来酐和富马酸。
适合本发明使用的第二类多官能相容剂化合物的特征是:既包含(a)通式(OR)代表的基团,其中R是氢或烷基、芳基、酰基或羰基二氧基,又包含(b)至少两个选自下列的相同或不同基团:羧酸、酰基卤、酸酐、酰基卤酸酐、酯、原酸酯、酰胺、酰亚胺基、氨基,及其各种形式的盐。这类相容剂当中的典型是以下面的通式代表的脂族多羧酸、酸酯及酸酰胺:
(RⅠO)mR(COORⅡ)n(CONRⅢRⅣ)s
其中R是线型或支链饱和脂族烃链,包含2~20,优选包含2~10个碳原子;RⅠ选自氢或含1~10个,优选1~6个,最优选1~4个碳原子的烷基、芳基、酰基或羰酰二氧基的基团,而以氢为特别优选的;每个RⅡ独立地选自氢或含1~20个碳原子,优选1~10个碳原子的烷基或芳基;每个RⅢ及RⅣ主要是独立地选自氢或1~10个,优选1~6个,最优选1~4个碳原子的烷基或芳基;m等于1,(n+s)大于或等于2,优选等于2或3;n和s每一个大于或等于0;其中(ORⅠ)位于羰基的α位或β位,且至少有两个羰基由2~6个碳原子隔开。显然,RⅠ、RⅡ、RⅢ、RⅣ,当相应取代基所含的碳原子数小于6时,则不可能是芳基。
合适的多羧酸的例子包括柠檬酸、苹果酸及2-十六烷基柠檬酸;包括其各种各样的市售形式,如无水及水合酸。其中,柠檬酸是另一种优选的相容剂。可用于本发明的酯的例子包括,如乙酰基柠檬酸酯及柠檬酸单-和/或二-硬脂基酯等。可用于本发明的合适酸酰胺包括,例如N,N’-二乙基柠檬酸酰胺、N-苯基柠檬酸酰胺、N-十二烷基柠檬酸酰胺、N,N’-二(十二烷基)柠檬酸酰胺以及N-十二烷基苹果酸酰胺。尤其优选的衍生物是上述多羧酸的盐,包括与胺的盐和/优选地,相应的碱金属及碱土金属盐。合适的盐的例子包括苹果酸钙、柠檬酸钙、苹果酸钾以及柠檬酸钾。
第三类适用于本发明的多官能相容剂化合物的特征是,在分子中既包含(a)酰卤基团,最优选酰氯基团,又包含(b)至少一种羧酸、酸酐、酯、环氧、原酸酯或酰胺基团,优选羧酸或酸酐基团。这一类相容剂中的例子包括偏(即1,2,4-)苯三酐酰氯,氯甲酰基琥珀酸酐、氯甲酰基琥珀酸、氯甲酰基戊二酸酐、氯甲酰基戊二酸、氯乙酰基琥珀酸酐、氯乙酰基琥珀酸、偏苯三酸酰氯以及氯代乙酰基戊二酸。这当中,偏苯三酐酰氯是优选的。而特别优选的是,让这类相容剂与至少一部分聚苯醚预先反应,于是,该相容剂便是PPE-官能化的化合物了。
上述的相容剂在美国专利4,315,086、4,600,741、4,642,358,4,826,933、4,927,894、4,980,424、5,041,504以及5,115,042中有更详尽的描述。
上述相容剂可单独使用或以它们的各种不同组合形式使用。而且,它们可直接加入到熔体共混物中,或者与PPE及聚酰胺中之一或二者乃至与本发明组合物制备中使用的其他树脂材料,预先进行反应。对于许多上述相容剂,特别是采用多官能化合物,若让至少一部分相容剂,或者在熔体中或者在适当溶剂的溶液中,与全部或部分PPE预先反应,则可使相容性得到进一步改善。据信,这样的预反应使得相容剂与聚合物之间发生反应,从而如上所述,使PPE带上官能团。例如,PPE可预先与马来酐反应,生成酐官能化的PPE,它与聚酰胺的相容性较未官能化的PPE便有了改善。
当在制备本发明组合物中使用相容剂时,其初始用量应根据所选择的具体相容剂以及其加入到何种具体聚合物体系中去来决定。
在本发明的组合物中也可使用任何其他已知的相容剂体系。其他体系例如可见诸于美国专利4,866,144。
本发明的组合物还包含一种链烯-(甲基)丙烯酸烷基酯共聚物,它包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的部分。该链烯优选包含2~约6个碳原子,而(甲基)丙烯酸烷基酯中的烷基通常包含约1~约8个碳原子。这类聚合物可通过诸如乙烯及丙烯之类的烯烃,与各种(甲基)丙烯酸酯单体和/或各种以马来酸为基础的单体之间的共聚反应来制备。所谓(甲基)丙烯酸酯既指丙烯酸酯,也指相应的甲基丙烯酸酯类似物。所谓(甲基)丙烯酸酯单体既指(甲基)丙烯酸烷基酯单体,又指包含至少一种上述活性部分的各种(甲基)丙烯酸酯单体。
在优选的实施方案中,该共聚物是通过如下反应物的反应转化而来的:即以乙烯、丙烯或乙烯与丙烯的混合物作为链烯成分;以丙烯酸丁酯、丙烯酸己酯、或丙烯酸丙酯以及相应的(甲基)丙烯酸烷基酯作为(甲基)丙烯酸烷基酯单体成分,以及带有丙烯酸和马来酐的对应(甲基)丙烯酸烷基酯作为提供两种活性部分(即羧酸和酸酐)的单体。
该共聚物中的烯烃含量,以共聚物重量为基准,为约40~约90%(重量),优选约50~约70%(重量)。共聚物中(甲基)丙烯酸酯单体的含量,以共聚物重量为基准,为约10~约60%(重量),优选约30~约50%(重量)。包含活性部分的(甲基)丙烯酸酯单体在共聚物中通常占到,以共聚物重量为基准,约0.1~约15%(重量),优选约0.5~约10%(重量),最优选约1.0~约8%(重量)。
上述链烯-(甲基)丙烯酸烷基酯共聚物在本发明组合物中的含量可变化很大,然而其范围,以整个组合物重量为基准,一般为约1~约15%(重量),优选约2~约8%(重量)。优选的含量是使组合物式样板按照ISO6603-2,在-30℃经受落镖(falling dart)试验中击时表现出大于10毫米,优选大于12毫米的形变。还优选的是,上述链烯-(甲基)丙烯酸烷基酯的含量应使得相容化的PPE-聚酰胺组合物试样板按照ISO 6603-2,在-30℃经受落镖试验冲击时具有的断裂能大于40J,优选大于50J,更优选大于60J。在尤其优选的实施方案中,当试样板按照ISO 6603-2,在-30℃经受落镖试验冲击时,本发明组合物将具有大于40J的断裂能和大于10毫米的形变,更优选具有大于50J的断裂能和大于12毫米的形变,最优选具有大于60J的断裂能和大于12毫米的形变。
在优选的实施方案中,该链烯-(甲基)丙烯酸烷基酯共聚物由乙烯、丙烯酸丁酯、丙烯酸及马来酐转化而来,其中乙烯用量为约55~约65%(重量),丙烯酸丁酯用量为约30~约40%(重量),丙烯酸为约3~约7%(重量),以及马来酐为约0.08~约0.5%(重量),其中所有含量值均以共聚物重量为基准。在特别优选的实施方案中,链烯-(甲基)丙烯酸烷基酯共聚物由乙烯、丙烯酸丁酯、丙烯酸及马来酐转化而来,其中丙烯酸丁酯用量为约32~36%(重量),丙烯酸为约4.8~约5.8%(重量),以及马来酐为约0.55~约0.75%(重量),其余由乙烯转化而来,其中所有含量值均以共聚物重量为基准。
可以在按照本发明的组合物中加入一种或多种附加的抗冲击性改进剂。所有通常用于包含聚苯醚、聚酰胺或同时含有聚苯醚与聚酰胺的组合物的抗冲击性改进剂均可使用。尤其合适的是所谓嵌段共聚物,如三嵌段共聚物及二嵌段共聚物。可使用的二嵌段及三嵌段共聚物橡胶添加剂是:由一种或两种链烯基芳族嵌段,其典型例如是苯乙烯嵌段,与橡胶嵌段,例如是可部分氢化的丁二烯嵌段,所组成的热塑性橡胶。此类三嵌段共聚物与二嵌段共聚物的混合物对本发明组合物尤其有用。
当把至少一种嵌段共聚物与上述包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的链烯-(甲基)丙烯酸烷基酯共聚物组合起来使用时,据信,实施两相抗冲改性的方案是可能的。所谓两相抗冲改性是指,PPE相和聚酰胺树脂相各自包含一种抗冲击性改进剂。据信,链烯-(甲基)丙烯酸烷基酯共聚物上的(活性)部分将与聚酰胺树脂起反应,其作用方式与前面所描述的制备链烯-(甲基)丙烯酸烷基酯共聚物与聚酰胺树脂之间共聚物的相容剂相类似。
可制备出多种多样的相容化PPE-聚酰胺组合物,其中包含含量各异、种类各异的抗冲击性改进剂(即:包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的活性部分的(甲基)丙烯酸烷基酯共聚物;以及,还有所述的一种或多种嵌段共聚物)。就典型而言,抗冲击性改进剂的合计含量应为约1~约30%(重量),优选约2~约18%(重量),含量的基准为,连同前面所述的(甲基)丙烯酸酯共聚物的含量算在内的整个组合物重量。
本发明热塑性组合物还可包含任何下列的添加剂:增强纤维、填料、导电碳黑、碳纤维、碳原纤、稳定剂、染料、颜料、聚烯烃及阻燃剂。
本文援引的所有专利和专利申请均一律收作本文的参考文献。
下面,将通过实施例进一步说明本发明。
实验
在实施例中使用了如下材料:
PPE:聚(2,6二甲基-1,4-亚苯基醚),按在25℃,浓度0.6克/100毫升甲苯中的溶液测定,特性粘度为45毫升/克;
PA:一种聚酰胺6,6,按照ISO 307,以其硫酸溶液测定的比浓粘度为145毫升/克;
CA:柠檬酸;
SEBS:聚苯乙烯-聚(乙烯-丁烯)-聚苯乙烯嵌段共聚物;
SEP:聚苯乙烯-聚(乙烯-丙烯)嵌段共聚物;
EPDM-MAH:乙烯-丙烯-二烯共聚物橡胶,其中包含0.6%(重量)马来酐接枝物;以及
EBA-AA-MAH:乙烯、丙烯酸丁酯、丙烯酸及马来酐按60∶35∶4.8∶0.2重量比的共聚物。
将各种成分按照下表中所载的重量比例在双螺杆挤塑机中进行混炼,其中沿挤塑机长度的温度设定值介于约280~约310℃。螺杆速度为300rpm,排出量为10千克/小时。所有成分,除聚酰胺以外,均经由挤塑机主进料口加入;聚酰胺则在下游大约挤塑机长度的中点处加入。从挤塑机出来的线料由实验室设备造粒,并在约110℃干燥约3小时。干燥的颗粒注塑成标准ISO试样,以便测定物理性能。
表
试样 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
PPE | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 | 35.9 |
PA | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 | 48 |
CA | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 | 0.7 |
SEBS | 6 | 5 | 4 | 3 | 2 | 6 | 5 | 4 | 3 | 2 |
SEP | 7 | 6 | 5 | 4 | 3 | 7 | 6 | 5 | 4 | 3 |
EPDM-MAH | 2 | 4 | 6 | 8 | 10 | 0 | 0 | 0 | 0 | 0 |
EBA-AA-MAH | 0 | 0 | 0 | 0 | 0 | 2 | 4 | 6 | 8 | 10 |
性能:落镖:断裂能(J) | ||||||||||
23℃ | 74 | 65 | 66 | 63 | 50 | 73 | 73 | 70 | 63 | 52 |
-30℃ | 38 | 40 | 35 | 30 | 9 | 65 | 70 | 65 | 33 | 9 |
断裂形变(mm) | ||||||||||
23℃ | 23 | 22 | 22 | 21 | 16 | 25 | 26 | 25 | 25 | 26 |
-30℃ | 9 | 10 | 9 | 8 | 4 | 13 | 13 | 13 | 9 | 7 |
从表中结果可见,当包含了含有至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的部分的链烯-(甲基)丙烯酸烷基酯共聚物时,组合物在断裂能及形变方面将表现出,较包含只有一种活性基团的抗冲击性改进剂的组合物,显著的改善,尤其是在低温下。譬如,试样6与试样1的比较表明,试样6在-30℃测定得到的断裂能竟出乎意料地是试样1的1.7倍,试样6在-30℃测定得到的形变竟出乎意料地是试样1的1.4倍。从包含最高约8%(重量)含有至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的链烯-(甲基)丙烯酸烷基酯共聚物的组合物,也得到了与仅含一种活性部分的抗冲击性改进剂情况形成对照的出乎意料的类似结果。
Claims (11)
1.一种热塑性组合物,包含:
(a)一种相容化聚苯醚-聚酰胺树脂共混物,以及
(b)一种链烯-(甲基)丙烯酸烷基酯共聚物,它包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的部分,其中链烯-(甲基)丙烯酸烷基酯共聚物的含量,以整个组合物重量为基准,为约15%(重量)。
2.按照权利要求1的组合物,其中链烯-(甲基)丙烯酸烷基酯共聚物是乙烯、丙烯酸丁酯、丙烯酸及马来酐等单体的共聚物。
3.按照权利要求1的组合物,其中链烯-(甲基)丙烯酸烷基酯共聚物的含量,以整个组合物重量为基准,为约2~约8%(重量)。
4.按照权利要求1的组合物,它还包含至少一种选自三嵌段共聚物及二嵌段共聚物的嵌段共聚物。
5.按照权利要求1的组合物,其试样板按照ISO 6603-2,在-30℃进行落镖冲击测定得到的断裂能大于40J。
6.按照权利要求1的组合物,其试样板按照ISO 6603-2,在-30℃进行落镖冲击测定得到的形变值大于10毫米。
7.按照权利要求1的组合物,其中相容化聚苯醚-聚酰胺树脂共混物,采用选自马来酐、富马酸、柠檬酸、苹果酸及聚苯醚与偏苯三酐酰氯的反应产物的相容剂,进行了相容化。
8.按照权利要求1的组合物,它还包含选自增强纤维、填料、导电碳黑、碳纤维、碳原纤、稳定剂、染料、颜料、聚烯烃、阻燃剂及其混合物的添加剂、
9.用权利要求1的组合物制成的制品。
10.一种热塑性组合物,基本上包括以下成分:
(a)一种相容化聚苯醚-聚酰胺树脂共混物,以及
(b)一种链烯-(甲基)丙烯酸烷基酯共聚物,它包含至少两种选自羧酸、酸酐、环氧、噁唑啉及原酸酯的部分,其中链烯-(甲基)丙烯酸烷基酯共聚物的含量,以整个组合物重量为基准,为约1~约15%(重量)。
11.按照权利要求10的组合物,它还主要包括至少一种选自三嵌段共聚物和二嵌段共聚物的嵌段共聚物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US97494097A | 1997-11-20 | 1997-11-20 | |
US08/974,940 | 1997-11-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1220287A true CN1220287A (zh) | 1999-06-23 |
Family
ID=25522531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN98122527A Pending CN1220287A (zh) | 1997-11-20 | 1998-11-20 | 相容化聚苯醚-聚酰胺树脂共混物抗冲改性组合物 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0924261A1 (zh) |
JP (1) | JPH11241017A (zh) |
KR (1) | KR19990045412A (zh) |
CN (1) | CN1220287A (zh) |
BR (1) | BR9804710A (zh) |
CA (1) | CA2251056A1 (zh) |
SG (1) | SG71169A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101175974B (zh) * | 2005-05-10 | 2011-03-30 | 日本精工株式会社 | 磁编码器和具有磁编码器的滚柱轴承 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7022776B2 (en) * | 2001-11-07 | 2006-04-04 | General Electric | Conductive polyphenylene ether-polyamide composition, method of manufacture thereof, and article derived therefrom |
US7132063B2 (en) | 2003-08-16 | 2006-11-07 | General Electric Company | Poly(arylene ether)/polyamide composition |
US7166243B2 (en) | 2003-08-16 | 2007-01-23 | General Electric Company | Reinforced poly(arylene ether)/polyamide composition |
JP2009532574A (ja) * | 2006-04-05 | 2009-09-10 | サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ | ポリ(アリーレンエーテル)/ポリアミド組成物、方法、及び物品 |
CN101541477B (zh) * | 2006-11-21 | 2011-03-09 | 3M创新有限公司 | 研磨载体以及方法 |
GB2510550B (en) * | 2012-09-06 | 2017-05-17 | Devan Chemicals Nv | Methods and compositions for modifying polypropylene-based fibres |
EP3109282A4 (en) * | 2014-02-21 | 2017-03-08 | Asahi Kasei Kabushiki Kaisha | Polyamide resin composition, production method for polyamide resin composition, and molded article |
CN110248786B (zh) | 2017-02-03 | 2021-10-12 | 帝人株式会社 | 包含碳纤维和热塑性树脂的复合材料、使用该复合材料的成型体的制造方法以及成型体 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0247154A (ja) * | 1988-08-10 | 1990-02-16 | Eng Plast Kk | 耐熱性を改善された熱可塑性樹脂組成物 |
DE4030694A1 (de) * | 1990-09-28 | 1992-04-02 | Basf Ag | Thermoplastische formmassen auf der basis von polyoxymethylen und polyamid |
DE4306708A1 (de) * | 1993-03-04 | 1994-09-08 | Basf Ag | Formmassen auf der Grundlage von Polyarylenethern mit Anhydridgruppen |
DE4414044A1 (de) * | 1994-04-22 | 1995-10-26 | Basf Ag | Polyphenylenether/Polyamid-Formmassen |
JP3331743B2 (ja) * | 1994-05-13 | 2002-10-07 | 住友化学工業株式会社 | 熱可塑性樹脂組成物 |
DE69412102T2 (de) * | 1994-11-29 | 1999-03-11 | Gen Electric | Flammhemmende Polyamid-polyphenyleneether-Zusammensetzungen |
-
1998
- 1998-10-22 CA CA002251056A patent/CA2251056A1/en not_active Abandoned
- 1998-11-09 SG SG1998004610A patent/SG71169A1/en unknown
- 1998-11-11 EP EP98309249A patent/EP0924261A1/en not_active Withdrawn
- 1998-11-19 KR KR1019980049740A patent/KR19990045412A/ko not_active Application Discontinuation
- 1998-11-19 JP JP10328994A patent/JPH11241017A/ja active Pending
- 1998-11-19 BR BR9804710-8A patent/BR9804710A/pt not_active Application Discontinuation
- 1998-11-20 CN CN98122527A patent/CN1220287A/zh active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101175974B (zh) * | 2005-05-10 | 2011-03-30 | 日本精工株式会社 | 磁编码器和具有磁编码器的滚柱轴承 |
Also Published As
Publication number | Publication date |
---|---|
CA2251056A1 (en) | 1999-05-20 |
BR9804710A (pt) | 1999-12-14 |
SG71169A1 (en) | 2000-03-21 |
KR19990045412A (ko) | 1999-06-25 |
JPH11241017A (ja) | 1999-09-07 |
EP0924261A1 (en) | 1999-06-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1238426C (zh) | 导电聚苯醚-聚酰胺共混物 | |
US5145904A (en) | Reinforced colored thermoplastic molding materials based on polyphenylene ethers and polyamides | |
CN1625583A (zh) | 相容化的聚(亚芳基醚)/聚酰胺共混物的高流动性组合物 | |
JPS61502195A (ja) | 変性されたポリフェニレンエーテル―ポリアミド組成物の製造法 | |
EP0270796B1 (en) | Process for the preparation of Polyphenylene ether-polyamide resin compositions | |
JP3223792B2 (ja) | 熱可塑性樹脂組成物 | |
JPH0343307B2 (zh) | ||
CN1220287A (zh) | 相容化聚苯醚-聚酰胺树脂共混物抗冲改性组合物 | |
CN1068025C (zh) | 含有相容聚苯醚聚酰胺树脂掺混物的可挤塑的热塑性组合物 | |
JPH04227755A (ja) | ポリアミドブレンドの製造方法 | |
CN1436214A (zh) | 减振组合物及其方法 | |
JPH086028B2 (ja) | 改良されたポリフエニレンエーテルアロイ | |
US6107415A (en) | Uncompatibilized polyphenylene ether-polyamide compositions | |
EP0258421B1 (en) | Impact modified polyphenylene ether-polyamide compositions | |
CN1216560A (zh) | 基于间同结构的乙烯基芳族聚合物、低粘度聚酰胺和极性基团改性的聚亚苯基醚的热塑性模塑组合物 | |
JPH06200144A (ja) | 改良された流動性ポリマーアロイ | |
CN1106840A (zh) | 含有相容聚苯醚-聚酰胺基材树脂和一种或多种磷化合物的热塑组合物 | |
CN1225932A (zh) | 流动性改善的相容化聚苯醚-聚酰胺树脂共混物的组合物及其制法 | |
EP0237710A2 (de) | Thermoplastische Formmassen | |
HUT57246A (en) | Polyphenylether and polyamide-based thermoplastic compositions | |
EP0560447B1 (en) | Thermoplastic composition based on polyphenylene ether and polyamide | |
US5338789A (en) | Fiber-reinforced polyphenylene ether molding compositions and process for their preparation | |
SK66093A3 (en) | Thermoplastic composition based on polyphenylene ether and polyamide | |
JPS62246957A (ja) | 熱可塑性成形材料 | |
JP3358496B2 (ja) | 熱可塑性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |