WO1999037699A1 - Polymerisat greffe en micro-suspension et son procede de fabrication - Google Patents
Polymerisat greffe en micro-suspension et son procede de fabrication Download PDFInfo
- Publication number
- WO1999037699A1 WO1999037699A1 PCT/EP1999/000307 EP9900307W WO9937699A1 WO 1999037699 A1 WO1999037699 A1 WO 1999037699A1 EP 9900307 W EP9900307 W EP 9900307W WO 9937699 A1 WO9937699 A1 WO 9937699A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- component
- polymer
- microsuspension
- graft
- Prior art date
Links
- 229920000578 graft copolymer Polymers 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 35
- 229920000620 organic polymer Polymers 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- ISRJTGUYHVPAOR-UHFFFAOYSA-N dihydrodicyclopentadienyl acrylate Chemical compound C1CC2C3C(OC(=O)C=C)C=CC3C1C2 ISRJTGUYHVPAOR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims 1
- 239000000123 paper Substances 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 2
- 239000011162 core material Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- -1 peroxosulfates Chemical compound 0.000 description 7
- 229920005601 base polymer Polymers 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 229920002959 polymer blend Polymers 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004743 Polypropylene Chemical group 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives 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
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001155 polypropylene Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical class N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000819038 Chichester Species 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QUWPKSVNVOPLKX-UHFFFAOYSA-N octan-3-yl 2-sulfanylacetate Chemical compound CCCCCC(CC)OC(=O)CS QUWPKSVNVOPLKX-UHFFFAOYSA-N 0.000 description 1
- 229920005787 opaque polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
Definitions
- the invention relates to microsuspension graft polymers, processes for their preparation, their use and molding compositions containing them.
- Polymer blends often contain rubber-elastic graft copolymers which are said to give the polymer blends increased toughness. They can also serve as matting agents in the polymer blends.
- the graft copolymers can be prepared by the emulsion, suspension or microsuspension process.
- emulsion polymerization In emulsion polymerization, a heterogeneous reaction process, unsaturated monomers or monomer solutions are emulsified in a continuous phase, usually water, using an emulsifier system and polymerized with initiators which form free radicals. During the reaction, the emulsifier system forms micelles into which the at least partially water-soluble monomers from the emulsified monomer droplets migrate through the water phase.
- a corresponding method is described in the Encyclopedia of Polymer Science and Engineering, Volume 6, page 1 (1986), John Wiley and Sons, New York.
- microsuspension polymerization a liquid monomer mixture in water is distributed into very fine droplets using a protective colloid under strong shear.
- the droplets are polymerized with a polymerization initiator which is soluble in the droplets, and the small polymer particles obtained can subsequently be grafted.
- a corresponding one The method is described in DE-A-44 43 886.
- the graft copolymers described have a core to shell weight ratio of 60:40.
- microsuspension graft polymers do not have sufficient mattness and hardness in all applications.
- the object of the present invention is to provide microsuspension polymers which avoid the disadvantages of the known graft polymers and in particular show reduced light reflection, good dyeability and improved mechanical properties.
- microsuspension polymers composed of a graft core and a graft shell, in which the proportion of the graft shell is 45% by weight or more, based on the graft polymer, show reduced light reflection and advantageous mechanical properties, in particular advantageous hardness.
- Component AI preferably 25 to 55 wt .-%, particularly preferably 30 to 50 wt .-%.
- the proportion of component B1 is preferably 45 to 75% by weight, particularly preferably 50 to 70% by weight.
- microsuspension polymers A according to the invention show the above advantages in particular in comparison to microsuspension polymers which are composed of the same basic building blocks and in which the proportion of the graft shell is 40% by weight.
- the molding compositions according to the invention with the same rubber component (preferably polybutyl acrylate) content, a clearer matting effect can be observed with reduced scattering and an improvement in the mechanical properties.
- the lower scatter improves the colorability of the molding compositions containing the microsuspension polymers according to the invention.
- microsuspension polymerization is described, for example, in DE-A-4443 886.
- a method for producing the above microsuspension graft polymer is preferred
- the graft polymers according to the invention are preferably obtained as follows: the liquid monomer or liquid monomer mixture which is to be polymerized to give the particulate core polymer is mixed with water and a protective colloid.
- the (preferably water-insoluble) polymerization initiator is either also added now or only after the monomers have been dispersed, if appropriate also after the dispersion has been heated.
- a dispersion of tiny monomer droplets in water is produced from the heterogeneous mixture by intensive stirring at high speed with strong shear. Intensive mixers of any type are suitable for this.
- the desired particle size can be determined, for example, for diameters greater than 1 ⁇ m by taking light microscopic images and counting the number of particles which have a specific diameter.
- the polymerization is started by heating the dispersion.
- the reaction with moderate stirring, during which the droplets are no longer broken up, is continued until the conversion, based on the amount of monomers originally used, is above 50%, preferably above 85%.
- the reaction with the monomers from which the corresponding shells are to be produced is then continued in a manner known per se.
- the grafting can also be started when the polymerization conversion of the core monomers is still incomplete and above 50%, preferably above 85%.
- the shell and core form a more fluid transition compared to the sharper demarcation of core and shell polymer in the event that the core monomers are initially completely converted.
- the monomers are generally dispersed at a temperature of 0 to 100 ° C., preferably at about room temperature. As a rule, 0.4 to 10 kg of water are used per kg of monomers.
- the protective colloids suitable for stabilizing the dispersion are water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect against coagulation.
- Suitable protective colloids are cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic polymers such as
- Poly-N-vinylimidazole The amount of these protective colloids is preferably 0.1 to 5% by weight, based on the total mass of the monomers of the core.
- low molecular weight surface-active compounds for example of the anionic or cationic soap type, can also be used.
- Free radical initiators are suitable as polymerization initiators, in particular those which are soluble in the monomers and which preferably have a half-life of 10 hours when the temperature is between 25 and 150 ° C.
- Such initiators are described, for example, in the AKZO "Initiators for Polymer Production" product catalog.
- peroxides such as lauroyl peroxide, peroxosulfates, tert-butyl perpivalate and azo compounds such as azodiisobutyronitrile are suitable.
- oil-soluble radical formers preferably dilauroyl peroxide, benzoyl peroxide and 2,2'-azo-bis-isobutyronitrile
- water-soluble initiators such as hydrogen peroxide, potassium, ammonium and sodium peroxide and persulfates, can also be used, especially if smaller particles of less than 1.0 ⁇ m should be obtained.
- initiators can be used to produce the graft core and the graft shells.
- the amount of initiators is generally 0.1 to 2.5% by weight, based on the amount of monomers.
- reaction mixture preferably contains buffer substances, such as Na HPO 4 / NaH 2 PO or Na citrate / citric acid, in order to set an essentially constant pH.
- buffer substances such as Na HPO 4 / NaH 2 PO or Na citrate / citric acid
- molecular weight regulators such as ethylhexylthioglycolate or dodecyl mercaptan are generally added during the polymerization, in particular of the monomers that make up the shells.
- the temperature in the polymerization of the monomers of the core is generally 25 to 150 ° C., preferably 45 to 120 ° C.
- the shells are generally grafted onto the core at a temperature of 25 to 150 ° C., preferably 45 to 120 ° C.
- the lower limit values of these ranges correspond to the decomposition temperatures of the polymerization initiators used in each case.
- the microsuspension polymer AI has an average particle diameter of 0.08 to 100 ⁇ m, preferably 0.2 to 50 ⁇ m, particularly preferably 0.3 to 30 ⁇ m.
- the particle size can be determined using different methods. For example, it is determined by light scattering. The light scattering method, as available from Leeds & Northrop, North Wales, PA, is preferred. It can also be used with devices from Particle Data, Elmhurst, Illinois, USA, for example with the ELZONE 280PC system.
- Component AI preferably has a glass transition temperature of below 0 ° C, particularly preferably of below minus 10 ° C. Any suitable rubber-elastic polymers can be used.
- Component AI is preferably composed of components All to A13, the total weight of which is 100% by weight,
- the proportion of component All is preferably 60 to 100% by weight, particularly preferably 80 to 100% by weight.
- the proportion of component AI 2 is preferably 0 to 8% by weight, particularly preferably 0.1 to 6% by weight.
- the proportion of component AI 3 is preferably 0 to 35% by weight, particularly preferably 0 to 15% by weight.
- Component All is preferably a C 8 alkyl acrylate, particularly preferably n-butyl acrylate and / or 2-ethylhexyl acrylate. 0 to 50% by weight of component All can also be replaced by one or more of the following monomers Al 3: styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, C9-40-alkyl (meth) acrylate, C-Mo-aralky ⁇ met acrylate, C6-40-aryl (meth) acrylate, C ⁇ o-alkaryl nettyacrylate, ⁇ -olefins with 2 to 20 C atoms, polyisobutylenes with 3 to 50 isobutene units and optionally terminal vinyl or vinylidene group, polypropylenes with terminal vinyl - Or vinylidene group with 3 to 100 propylene units, oligohexene, oligooctadecene, C o-
- Additional monomers are C 7 - 2 o-aralkyl (meth) acrylate, C. 6 2 o-aryl (meth) acrylate, C7-20-alkaryl (meth) acrylate, ⁇ -olefins with 6-20 C atoms, polyisobutylenes with 5-30 isobutene units and possibly terminal vinyl or vinylidene group, polypropylenes with terminal Vinyl or vinylidene group with 7-30 propylene units, C ⁇ o-2 4 -alkyl vinyl ether and vinyl esters of saturated C10- 2 -carboxylic acids.
- crosslinking monomers can be used as component Al 2.
- crosslinking monomers include bifunctional and polyfunctional comonomers such as butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols such as ethylene glycol or butane-1,4-diol, 1,4 - divinylbenzene and triallyl cyanurate.
- the acrylic ester of tricyclodecenyl alcohol (dihydrodicyclopentadienyl acrylate) and allyl esters of acrylic acid and methacrylic acid are particularly preferably used.
- Component B1 is in particular styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid ester or mixtures thereof. If the microsuspension graft polymers are to be incorporated into matrix polymers, the outer shell and the matrix polymer are preferably compatible or partially compatible.
- the particulate graft polymers according to the invention serve mainly as additives to brittle, thermoplastic, macromolecular base materials (polymer matrix).
- the invention also relates to a molding composition of this type comprising components A to D, the total weight of which is 100% by weight,
- a 0.5 to 80% by weight, preferably 1 to 60% by weight, preferably 1 to 50% by weight, of at least one microsuspension graft polymer described above as component A, a ': 0 to 79.5% by weight. %, preferably 0 to 59% by weight of an ASA, ABS or AES polymer of component A ', b: 20 to 99.5% by weight, preferably 40 to 99% by weight, of a polymer matrix, for example polyamide, polyester, polyoxymethylene, polycarbonates, polysulfone, polyether sulfone or preferably polymers made from styrene, - methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component B, c: 0 to 50% by weight, preferably 0 to 40 % By weight, fibrous or particulate
- component C Fillers or their mixtures as component C, and d: 0 to 50% by weight, preferably 0 to 40% by weight, of further additives as component D.
- component A By adding component A, the impact strength of the molding composition is improved. On the other hand, caused by diffuse reflection (scattering) of the light on the large particles, molding compounds with reduced surface gloss and correspondingly matt molded parts are obtained.
- the rubber-elastic particles are incorporated into the melt of the matrix B, so that the molding material formed from the thermoplastic matrix
- base polymers compatible, the rule is that their outer graft shell is partially compatible or compatible with the base polymer and preferably consists of the same or as similar a material as the base polymer.
- the technically most important base polymers are homopolymers of styrene, methyl acrylate, (C-alkyl methacrylates and acrylonitrile, copolymers of these monomers and other comonomers such as methacrylonitrile, ie these monomers and monomer mixtures are suitable for building up the external ones, depending on the structure of base polymer B. Graft bowl.
- the outer shell is to be relatively hard, intermediate shells made of a less hard material can be recommended.
- the first hard grafting shell can be followed by a shell made of soft material, for example the core material, as a result of which the properties of the thermoplastic molding compositions produced from the matrix B and the graft polymer particles A and the molding bodies produced therefrom can often be further improved.
- the relationships between the nature of both components in the molding compositions and the material properties correspond, moreover, to those known for the base material and graft polymers which are prepared by emulsion polymerization.
- base materials B other than those mentioned, e.g. Polyesters, polyamides, polyvinyl chloride, polycarbonates and polyoxymethylene. In these cases, compatible and partially compatible graft shells can be easily determined through a few preliminary tests.
- Compatibility is understood as miscibility at the molecular level.
- One polymer is considered to be compatible with another if the molecules of both polymers are statistically distributed in the solid state, i.e. if the concentration of a polymer along any vector neither increases nor decreases. Conversely, it is considered incompatible if two phases are formed in the solid state, which are separated from one another by a sharp phase boundary.
- a vector intersecting the phase interface suddenly increases the concentration of one polymer from zero to 100% and that of the other from 100% to zero.
- solubility parameter as a quantitative measure is e.g. the Polymer Handbook, ed. J. Brandrup and E.H. Immergut, 3rd edition, Wiley, New York 199, p. VH / 519-VII / 550.
- the graft polymers (A) according to the invention are generally used in amounts of 0.5 to 80, preferably 1 to 60, particularly preferably 1 to 50% by weight, based on the amount of their mixture with the base polymer Shaped bodies from such mixtures are very light-friendly and therefore particularly matt to - 12 -
- concentrations of 0.5 to 10% by weight of the graft polymers A are recommended. Since at these low concentrations only a relatively small increase in impact strength would be achieved, conventional, Use very fine-particle rubber-elastic modifiers in the usual amounts for this, minus the amount of the graft polymer according to the invention used as a matting agent.
- the particles according to the invention achieve a matting effect without noticeably impairing mechanical properties, as can be observed with conventional matting agents such as chalk or silica gel.
- the protective colloids used in the production of the core polymers have, because of their higher molecular mass and larger space filling of the molecules, much less effort than the low molecular weight emulsifiers to migrate to the surface of the plastic. High molecular protective colloids are therefore far less likely to exude from a molded part.
- the molding compositions can contain fibrous or particulate fillers or mixtures thereof as component C.
- fibrous or particulate fillers or mixtures thereof are carbon fibers or glass fibers, for example made of E, A or C glass. They can preferably be equipped with a size and an adhesion promoter.
- Other fillers or reinforcing materials are glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite.
- the molding compositions can also contain additives of all kinds as component D.
- additives of all kinds as component D for example, Lubricants and mold release agents, pigments, flame retardants, dyes, stabilizers and antistatic agents, all of which are added in the usual amounts.
- the molding compositions according to the invention can be prepared by mixing processes known per se, e.g. by incorporating the particulate graft polymer into the base material at temperatures above the melting point of the base material, in particular at temperatures of 150 to 350 ° C. in conventional mixing devices. Films, fibers and molded articles with reduced surface gloss (mattness) and high impact strength can be produced from the molding compositions according to the invention. No separation of the polymer components occurs in the films, fibers and molded bodies.
- the particle size distribution of the microsuspension polymer was determined using an Elzone® 280PC device from Particle Data, Elmhurst Illinois, USA.
- the particle size of the emulsion polymer was measured using an ultracentrifuge.
- the D (50) value is the value at which 50 volume percent of the particles are larger and 50 volume percent of the particles are smaller than this value.
- the following batch was stirred under nitrogen with a Dispermat at 7000 rpm for 20 minutes. This approach was made twice.
- the Dispermat came from VMA-Getzmann GmbH, D-51580 Reichshof and was provided with a 5 cm tooth lock washer.
- the weight ratio of graft shell (polystyrene / acrylonitrile, SAN) to graft core (polymer of n-butyl acrylate and dihydrodicyclopentadienyl acrylate, PBA + DCPA) was 40:60.
- the D 5 was o-value of the particle size distribution of 2.5 in.
- Example 1 was repeated, but the ratio of graft shell to graft core was 50:50.
- Example 1 was repeated, but the ratio of graft shell to graft core was 60:40.
- Example 1 was repeated, but the ratio of graft shell to graft core was 70:30. - 16 -
- Rubber-elastic graft polymer (core cross-linked polybutyl acrylate, shell styrene-acrylonitrile copolymer), weight-average particle diameter approx. 90 nm.
- the completion of the monomer addition was left to react for an hour.
- the resulting latex had a solids content of 40% and a weight-average particle size d 5 o of 76 nm.
- the polymer dispersion containing the polymer from f2, was coagulated by adding a magnesium sulfate solution and mixed with the styrene / acrylonitrile copolymer fl in an extruder type ZSK 30 from Werner and Pfleiderer.
- the blends contained 50% by weight of component fl (PSAN) and 50% by weight of component f2 (emulsion graft rubber).
- the ASA molding compound was melted together with further polystyrene-acrylonitrile copolymer (al) in a ZSK 30 extruder from Werner and Pfleiderer (260 ° C.).
- the polymer suspensions from experiments 1 to 4 were pumped into this polymer melt and the water was drawn off along the extruder.
- the finished mixture was discharged from the extruder as a polymer strand and granulated.
- the amount of polybutyl acrylate from the micro-suspension polymer and emulsion polymer in the blends was kept constant at 28.8% by weight and 18.0% by weight.
- Example shell core% by weight ASA% by weight PSAN MS polymer light reflection% (1) scattering (2)% by weight from experiment £ 2 ⁇
- Example shell core% by weight ASA% by weight PSAN% by weight MS light reflection% A at 23 ° C kJ / - AKLbie 23 ° C kJ / - test number polymer 0) m ⁇ 2 280/60 ° C m ⁇ 2 280/60 ° C (4) f2 fl from experiment (3)
- the sample plates were measured both over a white and a black background using a VIS spectrophotometer (Ultrascan from Hunter). Using a computer program based on the Kubelka-Munk theory (based on DIN 53234), the specific scatter at the wavelengths between 400 and 700 nm was calculated from these measurements.
- a product that can be colored very well has minimal scatter.
- AKL Punch impact strength measured on standard small bars at 23 ° C according to DIN 53753-L-3-3.0 (edition 4/81). The standard small bars were injection molded at a polymer melt temperature of 280 ° C and a mold temperature of 60 ° C.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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EP99906161A EP1045871A1 (fr) | 1998-01-21 | 1999-01-19 | Polymerisat greffe en micro-suspension et son procede de fabrication |
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DE1998102110 DE19802110A1 (de) | 1998-01-21 | 1998-01-21 | Mikrosuspensionspfropfpolymerisate und Verfahren zu ihrer Herstellung |
DE19802110.0 | 1998-01-21 |
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US9745456B2 (en) | 2013-03-19 | 2017-08-29 | Ineos Styrolution Group Gmbh | Matt weather-resistant molding masses for extrusion methods |
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DE60142993D1 (de) * | 2000-03-24 | 2010-10-14 | Cray Valley Sa | Zusamensetzungen mit wässrigen Polymerdispersionen, filmbildend ohne Lösungsmittel, zur Behandlung von Leder |
KR102256898B1 (ko) * | 2014-04-02 | 2021-05-31 | 이네오스 스티롤루션 그룹 게엠베하 | 개선된 기계적 특성을 지닌 열가소성 성형 조성물의 제조 방법 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR1526148A (fr) * | 1967-04-10 | 1968-05-24 | Ugine Kuhlmann | Compositions thermoplastiques de moulage résistant au choc et au vieillissement |
DE4443886A1 (de) * | 1994-12-09 | 1996-06-13 | Basf Ag | Kautschukelastische Pfropfpolymerisate |
-
1998
- 1998-01-21 DE DE1998102110 patent/DE19802110A1/de not_active Withdrawn
-
1999
- 1999-01-19 EP EP99906161A patent/EP1045871A1/fr not_active Withdrawn
- 1999-01-19 WO PCT/EP1999/000307 patent/WO1999037699A1/fr not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1526148A (fr) * | 1967-04-10 | 1968-05-24 | Ugine Kuhlmann | Compositions thermoplastiques de moulage résistant au choc et au vieillissement |
DE4443886A1 (de) * | 1994-12-09 | 1996-06-13 | Basf Ag | Kautschukelastische Pfropfpolymerisate |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9745456B2 (en) | 2013-03-19 | 2017-08-29 | Ineos Styrolution Group Gmbh | Matt weather-resistant molding masses for extrusion methods |
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