CN109401274A - 耐热树脂组合物及由此获得的成型制品 - Google Patents
耐热树脂组合物及由此获得的成型制品 Download PDFInfo
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- CN109401274A CN109401274A CN201811299887.3A CN201811299887A CN109401274A CN 109401274 A CN109401274 A CN 109401274A CN 201811299887 A CN201811299887 A CN 201811299887A CN 109401274 A CN109401274 A CN 109401274A
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- Prior art keywords
- resin
- polyamide
- heat resistant
- resin composition
- combination
- Prior art date
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- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 21
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 205
- 239000011347 resin Substances 0.000 claims abstract description 205
- 239000004952 Polyamide Substances 0.000 claims description 152
- 229920002647 polyamide Polymers 0.000 claims description 152
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 37
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002482 conductive additive Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- XZVDPRFYVGLYNO-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC=C.C=C.C1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC=C.C=C.C1=CC=CC=C1 XZVDPRFYVGLYNO-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 239000003973 paint Substances 0.000 abstract description 4
- 239000004922 lacquer Substances 0.000 abstract description 3
- 238000007591 painting process Methods 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 description 8
- -1 styrene (styrene)- Ethylene (ethylene)-butadiene (butadiene)-styrene (styrene) Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000012760 heat stabilizer Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 239000004698 Polyethylene Substances 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 2
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 2
- 241001247482 Amsonia Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229920006864 PPE/PS Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- ONUFRYFLRFLSOM-UHFFFAOYSA-N lead;octadecanoic acid Chemical compound [Pb].CCCCCCCCCCCCCCCCCC(O)=O ONUFRYFLRFLSOM-UHFFFAOYSA-N 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 description 1
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- YZAZXIUFBCPZGB-QZOPMXJLSA-N (z)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O YZAZXIUFBCPZGB-QZOPMXJLSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- UKTZJXRJZBVHKL-UHFFFAOYSA-N 2h-benzotriazole Chemical class C1=CC=C2NN=NC2=C1.C1=CC=C2NN=NC2=C1 UKTZJXRJZBVHKL-UHFFFAOYSA-N 0.000 description 1
- 229920001081 Commodity plastic Polymers 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920006100 Vydyne® Polymers 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
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- LJBCHOMMIHNUTK-UHFFFAOYSA-N butyl octadecanoate 2-butyloctadecanoic acid Chemical compound C(CCC)C(C(=O)O)CCCCCCCCCCCCCCCC.C(CCCCCCCCCCCCCCCCC)(=O)OCCCC LJBCHOMMIHNUTK-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- QPOIJJUKCPCQIV-UHFFFAOYSA-N diphenylmethanone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 QPOIJJUKCPCQIV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229940074096 monoolein Drugs 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/08—Front or rear portions
- B62D25/16—Mud-guards or wings; Wheel cover panels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L25/14—Copolymers of styrene with unsaturated esters
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- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
实施方案涉及一种耐热性有所提高的耐热树脂组合物及由此获得的成型制品,由于实施方案的树脂组合物具有高耐热性,所以即便经过诸如在线涂饰工序(painting process)这样的205℃以上的工序,也不会变形,形成优异外观,因此,可以有效地用于例如各种运送手段的外部材料或电气电子产品的壳体等。
Description
技术领域
实施方案涉及一种耐热性有所提高的树脂组合物及由此获得的成型制品,具体涉及一种可适用于对耐热性有要求的运送手段的外部材料、电气电子部件的壳体等的树脂组合物。
背景技术
虽然塑料材料的耐热性、耐燃性等性能相比金属或陶瓷材料差,但由于轻并且具有优异的加工性,从而广泛用于生活用品、汽车、电气、电子、产业领域等。
例如,聚酰胺(polyamide,PA)树脂是一种由重复的酰胺键(-CO-NH-)构成主链的线性聚合物材料,也称为尼龙树脂,由于机械性能,特别是耐药品性、耐摩擦性、耐磨耗性等优异,除了一般泛用塑料(commodity plastics)之外,还作为工程塑料(engineeringplastics)的材料被广泛使用。此外,聚苯醚(polyphenylene ether,PPE)也因为热变形温度(heat deformation temperature,HDT)高且电气特性及机械性能优异而作为工程塑料的材料被广泛使用。
所述塑料树脂,特别是PPE树脂,相比单独使用,更多是与其他塑料材料一起使用。像这样与其它树脂一起使用时,可以补偿各构成树脂的短处,从而能够满足目标用途要求的物理性能。
例如,当PPE与聚苯乙烯(polystyrene,PS)、聚酰胺(PA)等树脂一起使用时,除了PPE的物理性能之外,还可以获得PS、PA的耐冲击性、耐化学性等物理性能。特别是,已知PPE/PS、PPE/PA的组合表现出耐热性、耐冲击性、耐化学性等物理性能达到良好的平衡,从而适用于高尔夫球车、摩托车、汽车等的外部材料、电气电子产品的壳体等。
然而,尽管有这些优点,但是由于现有塑料材料本身的耐热限制,PPE/PS及PPE/PA混合树脂不但难以适用于在185℃以上或195℃以上的高温下进行的工序,例如,在线涂饰(on-line painting)工序,即便适用,也存在工序只能在比上述温度低的温度下进行的问题(参照韩国专利公开第2016-0121383号)。
因此,对具有更高的耐热性而适用于各种用途的塑料材料的研究仍在持续。
发明要解决的课题
实施方案欲提供一种树脂组合物,其维持聚苯醚(polyphenylene ether)及聚酰胺(polyamide)各自本来的优异性能,并具有汽车、摩托车等运送手段的外部材料或电气电子产品的壳体等要求的高耐热性,特别是即便经过205℃以上的高温工序,也不会变形,形成优异外观。
发明内容
实施方案提供一种耐热树脂组合物,其包含聚苯醚(PPE)树脂及聚酰胺(PA)树脂,所述聚酰胺(PA)树脂包含第一聚酰胺(PA)树脂单一树脂或第一聚酰胺(PA)树脂及第二聚酰胺(PA)树脂的混合树脂,所述第一聚酰胺(PA)树脂的熔点比所述第二聚酰胺(PA)树脂的熔点高20℃乃至100℃。
此外,实施方案提供由所述耐热树脂组合物射出成型的成型制品。
发明效果
本实施方案的耐热树脂组合物具有高耐热性,即便经过诸如汽车在线涂饰工序这样的205℃以上的工序,也不会变形,形成优异外观,因此,有效地应用于汽车外部材料、特别是汽车用塑料挡泥板(plastic fender)的制造。
发明的最佳实施方式
实施方案提供一种耐热树脂组合物,其包含聚苯醚(PPE)树脂及聚酰胺(PA)树脂,所述聚酰胺(PA)树脂包含第一聚酰胺(PA)树脂单一树脂或第一聚酰胺(PA)树脂及第二聚酰胺(PA)树脂的混合树脂。此时,所述第一PA树脂和所述第二PA树脂具有彼此不同的熔点,并且第一PA树脂的熔点可以比第二PA树脂的熔点高20℃乃至100℃。
所述PPE树脂可以是聚苯醚聚合物、反应性单体与聚苯醚聚合物反应的改性聚苯醚聚合物或它们的混合物。
所述PPE树脂可具有0.5乃至2,例如0.8乃至1.5,例如0.8乃至1.2的比重,并且可具有180℃乃至220℃,例如180℃乃至210℃,例如190℃乃至210℃的玻璃化转变温度。此外,所述PPE树脂可具有8×10-6乃至8×10-4,例如8×10-5乃至8×10-4的线性膨胀系数,并且可具有0.01%乃至0.1%,例如0.01%乃至0.08%,例如,0.02%乃至0.08%的吸水率。所述吸水率是在23℃下以饱和状态为基准进行测量的值。所述PPE树脂可以直接制备或者从Bluestar公司等供应商处购买后使用,但并不限定于此。
所述PA树脂可以是将氨基酸(amino acid)、内酰胺(lactam)、二胺(diamine)、二羧酸(dicarboxylic acid)或它们的组合作为主要单体成分进行聚合而获得的聚合物。例如,所述PA树脂可以单独或者以它们的混合物的形式包含衍生自上述主要单体成分的PA均聚物或共聚物。
具体地,所述PA树脂可以是单一的第一PA树脂,或者可以是所述第一PA树脂和所述第二PA树脂的混合树脂。就PA树脂而言,根据它的碳数、化学结构等,市场上销售的有约13种树脂,并且各自的物理性质不同。
所述第一PA树脂和所述第二PA树脂具有彼此不同的碳数和化学结构,通过适当调节这些,可实现所述耐热树脂组合物的目标性能。
所述第一PA树脂是熔点高于所述第二PA树脂的高熔点树脂,其熔点可以是约280℃乃至约320℃,例如,可以是约290℃乃至约320℃,例如,可以是约295℃乃至约320℃。
在一个实施方案中,所述耐热树脂组合物可包含作为PA树脂的第一PA树脂和第二PA树脂的混合树脂,第一PA树脂的熔点在上述范围内,第二PA树脂的熔点比这低20℃乃至100℃。
在另一个实施方案中,所述耐热树脂组合物可包含作为PA树脂的第一PA树脂单一树脂,其熔点在上述范围内。
在大气中的平衡状态下,所述第一PA树脂的含水率可以是3%乃至3.5%,在大气中的平衡状态下,所述第二PA树脂的含水率可以是2%乃至2.8%。然而,所述第一PA树脂由于额外的吸湿性而具有比所述第二PA树脂更低的尺寸变化率。其结果,将包含这个的树脂组合物用于运送手段的外部材料或电气电子产品的壳体时,可体现优异的尺寸稳定性。
所述第一PA树脂的重均分子量可以是约190g/mol乃至约200g/mol,所述第二PA树脂的重均分子量可以是约210g/mol乃至约230g/mol。
在一个实施方案中,所述第一PA树脂可以是己二酸(adipic acid)和具有碳数为3~5的亚烷基(alkylene group)的二胺(diamine)的共聚物,所述第二PA树脂可以是己二酸和具有碳数为6~8的亚烷基的二胺的共聚物;或者是己内酰胺(caprolactam)的开环聚合物。
在一个实施方案中,所述第一PA树脂可以是聚酰胺46树脂,所述第二PA树脂可以是聚酰胺66树脂或聚酰胺6树脂。在另一个实施方案中,所述第一PA树脂可以是聚酰胺46树脂,所述第二PA树脂可以是聚酰胺66树脂。
以树脂组合物的总重量为基准,所述树脂组合物可包含5wt%乃至80wt%、10wt%乃至70wt%、或者10wt%乃至60wt%的所述PPE树脂。另外,以树脂组合物的总重量为基准,所述树脂组合物可包含1wt%乃至80wt%、或者4wt%乃至80wt%的所述第一PA树脂。此外,以树脂组合物的总重量为基准,所述树脂组合物可包含0wt%乃至80wt%、或者0wt%乃至75wt%的所述第二PA树脂。
再者,所述聚苯醚(PPE)树脂、所述第一聚酰胺(PA)树脂和所述第二聚酰胺(PA)树脂的重量比可以是5乃至80:1乃至80:0乃至80。或者,所述聚苯醚(PPE)树脂、所述第一聚酰胺(PA)树脂和所述第二聚酰胺(PA)树脂的重量比可以是10乃至60:4乃至80:0乃至80。
具体地,所述PPE树脂和所述PA树脂的重量比可以是1:0.1乃至10、1:0.2乃至10、或者1:0.2乃至8。当所述PA树脂为第一PA树脂和第二PA树脂的混合树脂时,所述第一PA树脂和所述第二PA树脂的重量比可以是1:0.1乃至20、1:0.5乃至20、或者1:0.5乃至15。当含量在上述范围内时,本实施方案的树脂组合物可具有205℃以上的低载荷热变形温度。
更具体地,所述PPE树脂和所述PA树脂的重量比可以是1:0.1乃至10,所述PA树脂为第一PA树脂和第二PA树脂的混合树脂,所述第一PA树脂和所述第二PA树脂的重量比可以是1:0.1乃至20。
另外,所述PPE树脂和所述PA树脂的重量比可以是1:0.2乃至8,所述PA树脂为第一PA树脂和第二PA树脂的混合树脂,所述第一PA树脂和所述第二PA树脂的重量比可以是1:0.5乃至15。
进一步,所述PPE树脂和所述PA树脂的重量比可以是1:0.2乃至8,所述PA树脂为第一PA树脂和第二PA树脂的混合树脂,所述第一PA树脂和所述第二PA树脂的重量比可以是1:0.5乃至15。
所述树脂组合物还可以包含抗冲增强剂,所述抗冲增强剂包含苯乙烯(styrene)-乙烯(ethylene)-丁二烯(butadiene)-苯乙烯(styrene)(SEBS)树脂、马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯(MA-SEBS)树脂、或它们的混合物。所述SEBS及MA-SEBS用于改善PA树脂的尺寸稳定性、相容性、耐热性、耐化学性、成型加工性、抗冲击性等物理性质。
以所述树脂组合物的总重量为基准,所述抗冲增强剂的含量可以是2wt%乃至25wt%、或者4wt%乃至20wt%。当含量在上述范围内时,抗冲增强剂可以改善尺寸稳定性、耐化学性、耐冲击性、成型加工性等,且不会降低耐热性。
此外,根据需要,所述树脂组合物还可以包含相容剂、抗氧化剂、润滑剂、光稳定剂、光吸收剂、导电添加剂等添加剂。
具体地,所述树脂组合物,作为相容剂,可包含马来酸(maleic acid)、马来酸酐(maleic anhydride,MA)、富马酸(fumaric acid)、柠檬酸(citric acid)、柠檬酸酐(citric anhydride)或它们的混合物,以改善组合物之间的相容性。更具体地,所述相容剂可包含极性化合物,例如,可包含马来酸酐、柠檬酸或它们的混合物。这些与PPE树脂反应形成嵌段共聚物,从而改性PPE树脂以赋予相容性,并增强冲击强度。以所述树脂组合物的总重量为基准,所述相容剂的含量可以是0.01重量%乃至1重量%、0.01重量%乃至0.8重量%、0.05重量%乃至1重量%、0.05重量%乃至0.8重量%、或者0.1重量%乃至0.5重量%。
另外,所述树脂组合物可包含抗氧化剂,以便抑制高温过程中组合物的氧化或热解。所述抗氧化剂不受限制,只要是本领域常用的即可,例如,可以是IrganoxTM 1010、IrganoxTM 1076、3,5-二(叔丁基)-4-羟基甲苯(BHT)、IrgafosTM168、CyanoxTM 2246、CyanoxTM LTDP、CyanoxTM STDP、CyanoxTM MTDP、UltranoxTM 626、MarkTM 260等。以所述树脂组合物的总重量为基准,所述抗氧化剂的含量可以是0.01重量%乃至0.5重量%、或者0.1重量%乃至0.3重量%。
所述树脂组合物可包含金属硬脂酸盐(metal stearate)类润滑剂、酰胺(amide)类润滑剂、石蜡(paraffin)类润滑剂、酯(ester)类润滑剂等,以便在加热成型树脂时增加流动性,使得加工变得容易。例如,所述润滑剂可以是乙撑双硬脂酰胺(ethylene bisstearamide,EBS)、褐煤蜡(montan wax)、聚乙烯蜡(polyethylene wax,PE wax)、聚丙烯蜡(polypropylene wax,PP wax),石蜡(paraffin wax)、低分子量乙烯-乙酸乙烯共聚物(ethylene-vinyl acetate copolymer)(EVA)、硬脂酸(stearic acid)、油酸(oleicacid)、鲸蜡醇(cetyl alcohol)、油酸酰胺(oleamide)、芥酸酰胺(erucamide)、硬脂酰胺(stearamide)、硬脂酸丁酯(butyl stearate)、甘油单硬脂酸酯(glycerolmonostearate)、甘油单油酸酯(glycerine monooleate)、硬脂酸十八醇酯(stearylstearate)、硬脂酸钙(calcium stearate)、硬脂酸钡(barium stearate)、硬脂酸铅(leadstearate)、硬脂酸镁(magnesium stearate)等。以所述树脂组合物的总重量为基准,所述润滑剂的含量可以是0.01重量%乃至0.5重量%、或者0.1重量%乃至0.3重量%。
所述树脂组合物可包含热稳定剂,以便改善耐热性。所述热稳定剂可以是卤化物热稳定剂,具体地,可以是氯化铜(I)、溴化铜(I)、溴化铜(II)、溴化钾、氯化铜(II)、碘化铜(I)、碘化铜(II)、碘化钾等。以所述树脂组合物的总重量为基准,所述热稳定剂的含量可以是0.01重量%乃至0.5重量%、或者0.1重量%乃至0.3重量%。
所述树脂组合物可包含光稳定剂、光吸收剂等,以便抑制热分解,具体地,可包含卤素(HALS)光稳定剂、苯并三唑(benzotriazole)类光吸收剂、二苯甲酮(benzophenone)类光吸收剂等。可包含微量的所述光稳定剂和光吸收剂,例如,以所述树脂组合物的总重量为基准,可包含0.01重量%乃至2重量%、或者0.05重量%乃至1重量%。
所述树脂组合物还可包含导电添加剂,所述导电添加剂包含碳纳米管、炭黑、碳纤维、石墨烯、金属粉末或它们的混合物。所述导电添加剂分散在所述树脂组合物中以赋予导电性。以所述树脂组合物的总重量为基准,所述导电添加剂的含量可以是0.1重量%乃至20重量%、或者0.5重量%乃至10重量%。
虽然所述碳纳米管的尺寸没有特别限制,但是直径可以是0.5nm乃至100nm、或者1nm乃至10nm,长度可以是0.01μm乃至100μm、或者0.5μm乃至10μm。在所述直径和长度范围内时,导电性和加工性更加优异。
除此之外,还可包含已知的可用于所述树脂组合物或其成型品的各种添加剂,其具体类型和获得方法是本领域技术人员公知的。
根据ASTM D648标准,对所述树脂组合物进行测量时,可具有205℃以上、205℃乃至250℃、或者205℃乃至240℃的低载荷热变形温度(参照测试例1)。此外,在23℃的温度和50%的相对湿度下,根据ISO 62标准,对所述树脂组合物进行测量时,可具有1.5%以下、0.5%乃至1.5%、或者0.7%乃至1.5%的吸湿率(参照测试例2)。
再者,实施方案还提供由所述树脂组合物射出成型的成型制品。具体地,所述成型制品可通过成型等加工步骤由所述树脂组合物获得。所述成型制品可以是诸如汽车、摩托车、高尔夫球车等运送手段的外部材料,具体地,所述成型制品可以是汽车用塑料挡泥板(fender),但是并不限定于此。此外,所述成型制品可以是电气电子产品的壳体,但是并不限定于此。
如上所述,由于本实施方案的树脂组合物具有高耐热性,所以即便经过205℃以上的工序,例如运送手段的外部材料或电气电子产品的壳体等的在线涂饰(on-linepainting)工序,也可以形成优异的外观而不变形,从而可以有效应用于各种用途。
[实施例]
在下文中,根据以下实施例更详细地描述本发明。然而,以下实施例仅用于例示本发明,本发明的范围并不限定于这些。
PPE树脂:PPE,Bluestar公司
第一PA树脂:聚酰胺46(熔点:290℃),Stanyl,DSM公司
第二PA树脂:聚酰胺66(熔点:264℃),Vydyne,Ascend公司
抗冲增强剂:SEBS树脂,G1651,Kraton公司
:MA-SEBS树脂,FG1901,Kraton公司
相容剂:马来酸酐(MA),Yongsan Chemicals公司
润滑剂:乙撑双硬脂酰胺(ethylene bis-stearamide,EBS),L-C 140P,LIONCHEMTECH公司
抗氧化剂:Irganox 1010,BASF公司
热稳定剂:碘化钾,Nowchem公司
实施例1乃至9及比较例1和2:制备树脂组合物
将PPE树脂、第一PA树脂、第二PA树脂与其它成分以下表1中所示的含量各自混合在一起以制备树脂组合物。具体地,在30kg/hr、330℃的条件下,使用32mm的双螺杆挤出机(Twin screw extruder)混合各成分以制备树脂组合物。
试验例1:低载荷热变形温度(heat deformation temperature;HDT)
使用170吨电动射出机,在300℃的射出温度和100℃的模具温度条件下将实施例1~9及比较例1~2的各树脂组合物射出成型,并根据ASTM D648标准,Edgewise,在4.6kgf的载荷下,对6.4mm×128mm的试样测量低载荷热变形温度。
试验例2:吸湿率
使用和所述试验例1相同的方法,将实施例1~9及比较例1~2的树脂组合物射出成型,并根据ISO 23标准,在温度为23℃、相对湿度为50%的条件下,对大小为60mm×60mm×2mm(宽×长×厚)的试样测量吸湿率。
【表1】
如上述表1所示,可确认以下内容,实施例1~9的树脂组合物均表现出205℃以上的低载荷热变形温度,并且表现出1.5%以下的低吸湿率。然而,比较例1~2的树脂组合物表现出比实施例低的低载荷HDT值,并且比较例1的树脂组合物表现出大于1.5%的吸湿率。
由此,从上述表1所示的结果可预想实施例的树脂组合物因为具有优异的耐热性,从而即便应用于205℃以上的高温工序,也不会引起变形。
Claims (13)
1.一种耐热树脂组合物,其包含聚苯醚(PPE)树脂及聚酰胺(PA)树脂,
所述聚酰胺(PA)树脂包含第一聚酰胺(PA)树脂单一树脂、或者第一聚酰胺(PA)树脂及第二聚酰胺(PA)树脂的混合树脂,
所述第一聚酰胺(PA)树脂的熔点比所述第二聚酰胺(PA)树脂的熔点高20℃乃至100℃。
2.如权利要求1所述的耐热树脂组合物,其特征在于,
所述第一聚酰胺(PA)树脂的熔点为280℃乃至320℃。
3.如权利要求1所述的耐热树脂组合物,其特征在于,
所述聚苯醚(PPE)树脂、所述第一聚酰胺(PA)树脂和所述第二聚酰胺(PA)树脂的重量比是10乃至60:4乃至80:0乃至80。
4.如权利要求1所述的耐热树脂组合物,其特征在于,
所述聚苯醚(PPE)树脂和所述聚酰胺(PA)树脂的重量比是1:0.1乃至10,
所述聚酰胺(PA)树脂为第一聚酰胺(PA)树脂和第二聚酰胺(PA)树脂的混合树脂,
所述第一聚酰胺(PA)树脂和所述第二聚酰胺(PA)树脂的重量比是1:0.1乃至20。
5.如权利要求1所述的耐热树脂组合物,其特征在于,
所述聚苯醚(PPE)树脂和所述聚酰胺(PA)树脂的重量比是1:0.2乃至8,
所述聚酰胺(PA)树脂为第一聚酰胺(PA)树脂和第二聚酰胺(PA)树脂的混合树脂,
所述第一聚酰胺(PA)树脂和所述第二聚酰胺(PA)树脂的重量比是1:0.5乃至15。
6.如权利要求1所述的耐热树脂组合物,其特征在于,
所述树脂组合物还包含抗冲增强剂,所述抗冲增强剂包含苯乙烯-乙烯-丁二烯-苯乙烯(SEBS)树脂、马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯(MA-SEBS)树脂、或它们的混合物。
7.如权利要求6所述的耐热树脂组合物,其特征在于,
以所述树脂组合物的总重量为基准,所述抗冲增强剂的含量是2wt%乃至25wt%。
8.如权利要求1所述的耐热树脂组合物,其特征在于,
所述树脂组合物还包含相容剂,所述相容剂包含马来酸酐、柠檬酸或它们的混合物。
9.如权利要求1所述的耐热树脂组合物,其特征在于,
所述树脂组合物还包含导电添加剂,所述导电添加剂包含碳纳米管、炭黑、碳纤维、石墨烯、金属粉末或它们的混合物。
10.如权利要求1所述的耐热树脂组合物,其特征在于,
在23℃的温度和50%的相对湿度下,根据ISO 62标准,对所述树脂组合物进行测量时,具有1.5%以下的吸湿率。
11.如权利要求1所述的耐热树脂组合物,其特征在于,
根据ASTM D648标准,对所述树脂组合物进行测量时,具有205℃以上的低载荷热变形温度。
12.一种成型制品,由权利要求1~11中任何一项所述的树脂组合物射出成型。
13.如权利要求12所述的成型制品,其特征在于,
所述成型制品为汽车用塑料挡泥板。
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