CN1450117A - Weatherable impact-resisting acrylic compositions - Google Patents
Weatherable impact-resisting acrylic compositions Download PDFInfo
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- CN1450117A CN1450117A CN 03110302 CN03110302A CN1450117A CN 1450117 A CN1450117 A CN 1450117A CN 03110302 CN03110302 CN 03110302 CN 03110302 A CN03110302 A CN 03110302A CN 1450117 A CN1450117 A CN 1450117A
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 22
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 14
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 11
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002362 mulch Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000012644 addition polymerization Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005034 decoration Methods 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 2
- 238000004049 embossing Methods 0.000 claims 1
- 239000011241 protective layer Substances 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000000806 elastomer Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 26
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 26
- 239000011159 matrix material Substances 0.000 description 24
- 239000004925 Acrylic resin Substances 0.000 description 23
- 229920000178 Acrylic resin Polymers 0.000 description 23
- 230000035939 shock Effects 0.000 description 20
- 239000004800 polyvinyl chloride Substances 0.000 description 12
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 241001093575 Alma Species 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004159 Potassium persulphate Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WRWTZGMZGSJTKK-UHFFFAOYSA-M S(=O)(=O)(O)S(=O)O.[Na+].[O-]O.C1(=CC=CC=C1)C(C)C Chemical compound S(=O)(=O)(O)S(=O)O.[Na+].[O-]O.C1(=CC=CC=C1)C(C)C WRWTZGMZGSJTKK-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- RXPKAZWARAPDMU-UHFFFAOYSA-M [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1 Chemical compound [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1 RXPKAZWARAPDMU-UHFFFAOYSA-M 0.000 description 1
- XTAGFKIZUCCRIY-UHFFFAOYSA-M [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1C(C)C Chemical compound [Na+].O=C.[O-]O.OSO.CC(C)C1=CC=CC=C1C(C)C XTAGFKIZUCCRIY-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
Disclosed is an improved weatherable thermoplastic composition. The composition is comprised of a copolymer of an alkyl acrylate or alkyl methacrylate and poly(methyl)methacrylate and a multi-stage, sequentially-polymerized impact modifier polymer. The copolymer is characterized by greater than 15 weight percent alkyl acrylate content. The multi-stage, sequentially-polymerized impact modifier is characterized by an elastomer stage, which is 55 percent by weight or greater of the impact modifier composition and is minimally crosslinked. The thermoplastic composition can be used in a wide range of film, sheet, or molded applications.
Description
The application requires the rights and interests of the U.S. Provisional Patent Application 60/369359 of submission on April 2nd, 2002.
Technical field
The present invention relates to (methyl) acrylic composition of Weatherable impact-resisting, said composition can be used to preparation (methyl) acrylic polymers goods or uses as polymeric matrix, and particularly PVC's covers coating.
Background technology
As everyone knows, acrylic composition and goods thereof because of its transparency, have chromatic colour, surface luster and anti-weather and be widely known by the people.But having low resistance to impact shock, they promptly have fragility also to be widely known by the people.Adding toughner or anti-impact modifier in acrylic composition has become and has made its more durable standing procedure.But, add the characteristic that these functional additives can reduce some needed acrylic material, for example add a large amount of rubber polymers and can reduce softening temperature and produce muddy.
People once repeatedly attempted improving acrylic composition by forming multipolymer, in order that change the physical properties of acrylic polymers.Other method comprises that use can improve the additive of physical properties (as resistance to impact shock), the polymkeric substance anti-impact modifier that promptly is commonly referred to.The polymkeric substance anti-impact modifier comprises many polymkeric substance, as natural and synthetic rubber, acrylic elastomer and terpolymer such as MBS (methyl methacrylate/Butadiene).
One type polymkeric substance anti-impact modifier is the acrylic composition of sequential polymerization, and it comprises core, intermediate phase (stage) and last phase, although exist between " layer " certain to mix.Usually, these are called as " core/shell " polymkeric substance.
There are many factors to determine the efficient and the effectiveness of any specific acrylic acid or the like core/shell anti-impact modifier.These factors comprise that this properties-correcting agent adheres in the above matrix with therein matrix or this properties-correcting agent, no matter it is to use separately or as the part of mulch (capstock) composition.And, far-reaching is the number of plies in per stage, every layer thickness and structure, every layer monomer composition, crosslink type and degree, grafted type and the degree of each layer, and the core of sequential polymerization/shell anti-impact modifier is a concentration in the initial polymer in matrix.Here Ding Yi matrix polymer is that initial polymer is the polymkeric substance that forms the large volume goods, as acrylic material plate or the mulch extruded.
The object lesson of core/shell anti-impact modifier can find in following referenced patent: United States Patent (USP) 3661994, United States Patent (USP) 3793402, United States Patent (USP) 4433103, United States Patent (USP) 4521568, United States Patent (USP) 4730023, United States Patent (USP) 5270397, United States Patent (USP) 6172135, United States Patent (USP) 5318737, European patent 0458520A2 and WO 00/08098.
Summary of the invention
Developed a kind of (methyl) acrylic composition that improves anti-weather, high impact strength that has.This composition comprises multipolymer and the polymethyl acrylic acid (methyl esters) and the anti-impact modifier polymkeric substance heterogeneous, sequential polymerization of alkyl acrylate or alkyl methacrylate.This multipolymer comprises the alkyl acrylate of at least 15 weight %.Anti-impact modifier heterogeneous, sequential polymerization has an elastomerics body phase, and it is at least 55 weight % or more anti-impact modifier composition, and is that bottom line is crosslinked.
Embodiment
Thermoplastic compounds of the present invention comprises the mixture of polymers of heterogeneous, the sequence preparation of the rigid thermoplastic multipolymer of about 40-90 weight % and 10-60 weight %.
The rigid thermoplastic multipolymer comprises the 50-80% monomers methyl methacrylate with another kind of alkyl acrylate or alkyl methacrylate copolymerization, and wherein alkyl has 1-4 carbon atom, and its content is 15-50 weight %.
Comprise a large amount of specially designed anti-impact modifiers of acrylic substrate needs of monomer (as ethyl propenoate) altogether, so that the toughness of utilizing matrix to improve.
Polymkeric substance heterogeneous, the sequence preparation is a kind of specially designed anti-impact modifier, it is characterized by:
(a) the optional still preferred first harder phase of inelastic body, its second-order transition temperature is higher than 25 ℃,
Its preparation is that polymerization contains the monomer that above-mentioned rigid thermoplastic multipolymer is used, together with 0-10 weight %
But copolymerizable functionality cross-linking monomer and the monomeric mixture of 0-10% copolymerized grafting, this can
The copolymerized grafting monomer has two and the unsaturated reactive group of more a plurality of polymerizable, as α, and β-no
The allyl group of saturated carboxylic acid or diacid, methacrylic or butene esters, described reactive group is to show
The different speed of work is participated in polyreaction.(b) comprising polymeric intermediate elastomeric phase under the product existence condition of first phase, described first comes mutually
Self-contained 50-99.9 weight % alkyl acrylate and/or alkyl methacrylate mixture (alkane
Base comprises 1-8 carbon atom) but, the single ethylenically unsaturated monomers of the copolymerization of 0-49.9 weight %,
But 0-0.5 above-mentioned being total to of the copolymerization polyfunctionality cross-linking monomer of weight % and 0.05-5.0 weight %
The monomer mixture of poly-grafted monomer, the feature that described elastomerics also has mutually is if monomer
Polymeric words under the condition that does not have the product that comprises first phase, its second-order transition temperature is
25 ℃ or lower; (c) a kind of and multiple harder mutually last, it be comprise first mutually and the product of intermediate phase have bar
Polymeric under the part, the monomer that this first phase and intermediate phase are used from above-mentioned rigid thermoplastic polymer mixes
Compound, the feature that described last phase also has is if it is not comprise first and middle
Polymeric words under the product existence condition of phase, its second-order transition temperature is higher than 50 ℃, described connecing
(they are not with significantly but the branch monomer has the unsaturated reactive group of two or more addition polymerizations
Speed is together participated in polyreaction), but and described cross-linking monomer has the insatiable hunger of many addition polymerizations
And group, all back these groups are all almost participated in polyreaction with identical speed.
Preferred multiphase polymer is a three-phase composition, and wherein the content of first phase (a) is 10-40 weight %; Be preferably 10-20 weight %, the content of second intermediate phase (b) is 45-70 weight %, preferably 50-60 weight %; The content of last phase (c) is 10-50 weight %, 20-40 weight % preferably, and all percentage ratio is all in the three-phase total polymer weight.
This multiphase polymer can prepare with the method that the polymkeric substance of known preparation multiphase sequence preparation is used, for example, by under the established polymer product existence condition formerly, the monomer mixture of phase after the letex polymerization.In this manual, term " the sequence letex polymerization " or " the sequence emulsion preparation " are meant the polymkeric substance (this term comprises multipolymer and homopolymer) for preparing in aqueous liquid dispersion or emulsion, at this moment, make afterwards monomer material polymerization under top or its existence condition of the latex that formerly forms (by the previous monomer material of polymerization and prepare mutually).In such polymerization, being close and combining closely afterwards in mutually previous.Therefore, in the preparation method of the polymkeric substance that the present invention prepares continuously, total particle content is substantially invariable after first phase polymerization reaction is finished, and promptly no longer includes new visibly different particle after forming the first phase particle.
Carry out polyreaction under the initiator existence condition, this initiator can comprise the polymerization regulator as chain-transfer agent.The ultimate size of the polymkeric substance of sequence preparation changes between the 100-350 nanometer, but preferable range is the 200-300 nanometer.
The type of used emulsifying agent and content are being controlled the particle diameter of intermediate phase latex particle.For most applications, soap class commonly used in letex polymerization can be used satisfactorily, as long as note using the minimum amount that obtains required result, and polymkeric substance is separated by condensing.
In in all polymerisable monomer gross weights that adds in mutually, the content of emulsion preferably is lower than 1 weight %, is preferably 0.1-0.6%.Useful emulsifying agent comprises common soaps, benzene sulfonamide acid esters such as benzene sulfonic acid sodium salt dodecyl ester, alkyl phenoxy polyethylene benzene sulfonate, sodium sulfate bay alcohol ester, long-chain amine salt, long-chain carboxylic acid's salt and sulfonate etc.Usually, emulsifying agent should be the compound of the alkyl that comprises 8-22 carbon atom (with the coupling of high polarity dissolving group), and described group comprises the group, sulfate hemiester group, sulfonate ester group, phosphoric acid part ester group of carboxy acid alkali's metal and ammonium etc.
Can comprise the polymerization starter of the suitable free radical of generation of significant quantity at each polymerisation medium in mutually, it or activate by heat or redox reaction.Preferred initiator is the initiator of thermal activation, as persulphate; But also can use redox initiator.The example of suitable oily molten water-insoluble initiator is following these combinations, as cumene hydroperoxide-Sodium Pyrosulfite, diisopropyl benzene hydroperoxide-sodium sulfoxylate formaldehyde, heavy tert.-butyl acetate-hydrosulphite, cumene hydroperoxide-sodium sulfoxylate formaldehyde etc.Also can use water soluble oxidized reduction initiator; Its initiator combination is Sodium Persulfate-sodium bisulfite, Potassium Persulphate-sodium sulfoxylate formaldehyde etc.
The multiphase sequence letex polymerization can be carried out in 0-125 ℃ temperature range, preferably 30-95 ℃.According to known practice, polymerisation medium can comprise chain-transfer agent (as tert-dodecyl mercaptan, sec-butyl thioalcohol, positive Dodecyl Mercaptan etc.), particularly is used for limiting the molecular weight of the phase that comprises rudimentary alkyl methacrylate, if desired Xian Zhi words.Effective usage quantity of radical initiator depends on monomer, temperature and adding method, but to add monomeric weight, initiator content in each polymerization mutually is generally about 0.001-2 weight %, but should be no more than 5 weight % (to add monomeric gross weight at all in mutually).
The rigid thermoplastic multipolymer comprises and another kind of alkyl acrylate or alkyl methacrylate, and the content of copolymerization is the monomers methyl methacrylate of 50-85%, and wherein alkyl has 1-4 carbon atom, and its content is 15-50 weight %.The molecular weight of multipolymer is about 400000 dalton of 50000-.Preferably contain the Jia Jibingxisuanyizhi and the methyl acrylate that are about 25 weight % in the monomer, its molecular weight is 200000-350000 dalton.Rigid thermoplastic polymer can comprise bulk polymerization, solution polymerization and letex polymerization by the standard method preparation of any preparation methacrylic ester and acrylate superpolymer.
The invention provides the product that a kind of toughness improves, it is based on the acrylic matrix that comprises a large amount of comonomers.Rubber toughened acrylic resin extensively is used in needs acrylic resin beneficial property (transparent, anti-weather etc.), but the unmodified acrylic resin of standard can't satisfy in the various uses of required toughness.The usual method of rubber toughened acrylic resin is to add acrylic acid or the like core-shell anti-impact modifier in resin.The most frequently used shock resistance acrylic resin comprises matrix ((MMA) forms by methyl methacrylate) and more a spot of multipolymer (about usually 0.5-10% methyl acrylate (MA) or ethyl propenoate (EA).Core-shell anti-impact modifier joins in the matrix with about 10-50 weight %.
Have been found that the common monomer content that improves in the matrix in the present invention, redesign the improving agent that new matrix is used then, can acquire much higher toughness.Comprise 25%EA as being total to the example that monomeric matrix comes to this.In the present invention, the anti-weather shock resistance acrylic resin that can be made into, its resistance to impact shock is 6 times of standard available shock resistance acrylic resin.
Another purposes of the present invention is as the PVC mulch.Rigid PVC is because its wearing quality is good, and cost is low, is widely used in the purposes of buildings outside, as siding board.But PVC understands owing to the effect of weather is degraded, thereby causes the change of color and/or the reduction of resistance to impact shock.Test the whole bag of tricks and overcome this defective.PVC comprises UV absorptivity pigment usually (as TiO
2).The PVC siding board is coextrusion mostly to be made, be thin and the high layer co-extrusion of pigment content be pressed onto thicker pigment content much less layer on.This upper strata provides the UV opacity to protect bottom, is unlikely because add a large amount of pigment in whole thickness to cause expense to rise.The anti-weather of PVC plate of the relative individual layer of these coextrusion structures is higher.But can fade, so need the mulch of a more anti-weather.A kind of in this material is acrylic resin.It is fine that acrylic resin is resisted the performance of outdoor weather effect, so expose the initial appearance that still can keep them after many years out of doors.A defective of acrylic resin is a resistance to impact shock.The ironed vinylformic acid coating material layer of co-extrusion can make the gained composite structure become fragile on PVC.This is not always the case for all impact modifications and unmodified acrylic acid or the like resin, and this has just limited them and has been used as the mulch of PVC.
But we find, can overcome this problem by using specially designed shock resistance acrylic resin.Acrylic resin must have enough toughness, and making breaks can not begin to take place (before at least obviously distortion taking place) at the acrylic resin layer.Have many methods can prepare this toughness acrylic resin: the shock resistance acrylic resin normally mixture of matrix polymer and anti-impact modifier constitutes.A large amount of anti-impact modifiers provide toughness, although add the amount of anti-impact modifier individual physical constraints are arranged.According to used processing units situation, 50-60% is the upper limit seemingly.20-45% more usually.
In most of shock resistance acrylic resins, matrix mainly is the methyl methacrylate (MMA) with a small amount of (1-10% usually) acrylate (normally MA or EA) copolymerization.Acrylate provides the enhanced thermostability.But, replace a spot of acrylate, if use a large amount of short chain acrylates (or methacrylic acid), the shock resistance product that obtains so will have enough toughness and come as the mulch on the PVC.Research work now shows that if EA is as being total to monomer, so approximately 25%EA obtains essential toughness.(other common monomer is expected to work on the different content.)
For the toughness of utilizing matrix to improve, need to add the anti-impact modifier that is in particular matrix design.We have found that we can not effectively improve the resistance to impact shock of toughness substrate as the anti-impact modifier in the standard shock resistance acrylic resin.Following change helps improving shock resistance:
Improve elastomer content
Reduce the linking agent/grafting agent content of elastomerics in mutually
Reduce the Tg of hard core
It should be noted that and it seems that the composition that need not to regulate shell mates the composition of matrix.We have obtained similar resistance to impact shock, and pipe shell is not 95/5 MMA/EA or 75/25 MMA/EA.But an optic advantage is the composition coupling matrix (refractive index match) that makes shell.Use the shell of minimum EA, having an advantage aspect efficiency of isolation and the powder properties.
Another one purposes of the present invention is so-called " in-mold decoration ", and wherein the clear acrylic polymer film is die-cut into required size and dimension.Die-cut also being commonly used to is used for the purposes of for example point-of-purchase display by plasticity plate and continuous coiled strip manufacture component.Die-cut is quick and economic machining process.Though acrylic resin has many character required in the in-mold decoration that are used in, and as outward appearance and anti-weather, when their shortcoming is die-cut brittle fracture can take place.Brittle fracture produces fragment and crack, is used in these purposes thereby get rid of it.So need a kind ofly to have gathered all beneficial characteristics of acrylic resin, can not produce the necessary flexible composition of cracking when die-cut but have.As mentioned above, add for example above-mentioned core/shell vinylformic acid anti-impact modifier, make the shock resistance acrylic resin and just can reach this purpose based on toughness substrate (as 25%EA).Property of toughness just as this film makes it the same as in-mold decorating, and it also can make film be used as free film or laminated film.In these purposes, the toughness of film has improved processing characteristics, and has reduced the possibility that film breaks or ruptures in processing and lamination step.In all these multi-layer compositions, the selection of matrix polymer only is subjected to obtaining accepting the restriction of adherent ability between acrylic composition and matrix.The example of these matrix polymers includes but not limited to: (methyl) acrylic polymers and multipolymer; Polycarbonate; Polyester and copolyesters; Vinyl polymer and multipolymer (comprising polyvinyl chloride); Styrene polymer and multipolymer (comprising acrylonitrile-butadiene-styrene copolymer, polystyrene and high-impact styrene).
Another purposes of the present invention is to be used for the high impact-resistant plate and as the casting resin.It is essential toughness in important some purposes that tradition impact modification acrylic resin does not have high impact strength.These purposes need be used other polymkeric substance, as polycarbonate or PETG, though their toughness is better than standard impact modification acrylic resin, and keep off the anti-weather or the optical transparence of acrylic resin.Can make the anti-impact propylene resin based on aforesaid toughness substrate, this material can provide these purposes essential toughness, keeps the advantage of anti-weather and optical transparence simultaneously.
More following embodiment are used for illustrating the present invention, but they far are not fully, can not limit the invention on the described details yet.Can make many other conversion and improvement with embodiment to specifications.
Embodiment 1
That this embodiment illustrates is heterogeneous, the preparation of the polymer composition of sequence preparation.
The ratio of three-phase is 15//65//20
Triphasic composition is
Phase 1:74.8/25/0.2 MMA/EA/ALMA
Phase 2:83.5/15.5/1.0 BA/Sty/ALMA
Phase 3:95/5 MMA/EA
The MMA=methyl methacrylate
The EA=ethyl propenoate
The BA=butyl acrylate
Sty=vinylbenzene
The ALMA=alkyl methacrylate
Use Phenylsulfonic acid potassium dodecyl ester as emulsifying agent emulsification in water the monomer feed of 34% phase 1, and use salt of wormwood control pH value, the use Potassium Persulphate carries out polymerization under the temperature that improves.Then the remainder of phase 1 is joined in the preformed polymer emulsion, use Potassium Persulphate to carry out polymerization under the temperature that improves, the add-on of controlling the soap class this moment prevents to form the new particle of more amount.Add 2 monomer mutually then, use Potassium Persulphate to carry out polymerization under the temperature that improves, the add-on that control soap this moment prevents to form the new particle of more amount.3 monomers use Potassium Persulphate to carry out polymerization under the temperature that improves mutually then, and the add-on that control soap this moment prevents to form the new particle of more amount.By condense, lyophilize or jet drying separate polymkeric substance.
Embodiment 2
Prepare polymkeric substance as embodiment 1 similar methods, different is that it has different phase ratios:
The ratio of three-phase: 12.5//54.2//33.3
The composition of phase is
Phase 1:74.8/25/0.2 MMA/EA/ALMA
Phase 2:83.5/15.5/1.0 BA/Sty/ALMA
Phase 3:95/5 MMA/EA
Embodiment 3
As embodiment 2 preparation polymkeric substance, different is in the aft section of third phase, adds 0.46 part of positive Dodecyl Mercaptan, in order to reduce molecular weight.
Embodiment 4 (comparison)
The polymkeric substance of embodiment 4 is the described polymkeric substance of 0wens (United States Patent (USP) 3793402), and existing preparation is with making comparisons.This polymer analog embodiment 1 preparation, different is composed as follows:
The ratio of three-phase: 35//45//20
The composition of phase is
Phase 1:95.8/0.4/0.2 MMA/EA/ALMA
Phase 2:80/18/2.0 BA/Sty/ALMA
Phase 3:96/4 MMA/EA
Embodiment 5-8
The polymkeric substance of embodiment 1-4 poly-with 60% (methyl methacrylate-be total to-ethyl propenoate) matrix is mixed, mixed in extrusion machine then.
| Form | ||
| Embodiment 5 | 40% embodiment 1 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 75/25 MMA/EA |
| Embodiment 6 | 40% embodiment 2 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 75/25 MMA/EA |
| Embodiment 7 | 40% embodiment 3 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 91/9 MMA/EA |
| Comparative example 8 | 40% embodiment 4 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 91/9 MMA/EA |
Embodiment 5-8 polymer in-mold is moulded 1/8, and " metal sheet is measured the crack and is begun to produce required energy in instrumented shock test
| Instrumentation falling dart test first energy-to-break | |
| Embodiment 5 | ????25J |
| Embodiment 6 | ????15J |
| Embodiment 7 | ????15J |
| Comparative example 8 | ????4.5J |
This table is clear to have shown that having best elastomer polymer is distributed in the advantage that comprises in the common monomeric PMMA matrix of volume EA.
Embodiment 9-10 (comparison)
Embodiment 9-10 polymkeric substance illustrates if elastomer polymer or matrix are changed in embodiment 7 polymkeric substance as the identical method preparation of embodiment 5-8, will lose high impact strength.
| Form | Instrumentation falling dart test first energy-to-break | ||
| Comparative example 9 | 40% embodiment 1 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 91/9 MMA/EA | ????6.4J |
| Comparative example 10 | 40% embodiment 4 | 60% poly-(methyl methacrylate-be total to-ethyl propenoate), 75/25 MMA/EA | ????4.7J |
Embodiment 11-13
Embodiment 11-13 preparation be that material with embodiment 5,6 and 8 is with the 4 close coextrusion materials that form on PVC of thickness of processing.About 46 Mills of the thickness of PVC.Press the GVHIT resistance to impact shock of ASTM-D4226-00 mensuration gained composite materials then.
| ????GVHIT | |
| Embodiment 11 | ????3.07?1b/mil |
| Embodiment 12 | ????2.43?1b/mil |
| Comparative example 13 | ????0.80?1b/mil |
Relative conventional acrylic resinoid (as comparative example 13), the advantage of material (as embodiment 11 and 12) is very tangible.Embodiment 13 can not satisfy the shock resistance requirement that the vinyl siding board is used.
Claims (14)
1. thermoplastic compounds of anti-the weather, it comprises multipolymer and polymethyl acrylic acid (first) ester and the multiphase sequence polymeric anti-impact modifier polymkeric substance of alkyl acrylate or alkyl methacrylate, the feature of described multipolymer is the alkyl acrylate that comprises greater than 15 weight %, the feature of described multiphase sequence polymeric anti-impact modifier is to have an elastomerics phase, described elastomerics is at least 55 weight % or more anti-impact modifier composition mutually, and is that bottom line is crosslinked.
2. thermoplastic compounds, it comprises
A. the rigid thermoplastic multipolymer of about 40-90 weight %, described multipolymer comprise 50-85 weight % methyl methacrylate and another kind of alkyl acrylate of 15-85 weight % or alkyl methacrylate, and described alkyl has 1-4 carbon atom,
The polymkeric substance of the multiphase sequence preparation of b. about 10-60 weight % is characterized in that:
(A) the Ren Xuan first non-resilient harder phase, its second-order transition temperature is higher than 25 ℃, its preparation is that polymerization comprises the above-mentioned monomer that 100-80 weight % rigid thermoplastic multipolymer is used, but but 0-10 weight % copolymerization polyfunctionality cross-linking monomer and the monomeric monomer mixture of 0 one 10 weight % copolymerized graftings, but but described copolymerized grafting monomer has two or more unsaturated reactive groups of addition polymerization of participating in polyreaction with remarkable different rates
(B) intermediate phase of polymeric elastomerics under the first phase existence condition, this comprise 50-99.9 weight % alkyl acrylate and/or alkyl methacrylate mixture (alkyl has 1-8 carbon atom) mutually but but but, the single ethylenically unsaturated monomers of 0-49.9 weight % copolymerization, 0-5.0 weight % copolymerization polyfunctionality cross-linking monomer and the monomeric monomer mixture of the above-mentioned copolymerized grafting of 0.05-5.0 weight %, the feature that described intermediate also has mutually is that its second-order transition temperature is 25 ℃ or lower if monomer polymeric under the condition that does not have first phase is talked about;
(C) at least a harder last phase, it is to derive from first polymeric mutually and in the presence of the intermediate phase of monomer mixture that rigid thermoplastic polymer uses, the feature that described last phase also has is, if monomer do not have first and the intermediate phase existence condition under polymeric words, its second-order transition temperature is higher than 50 ℃, but grafted monomer has two or more to show the unsaturated reactive group of addition polymerization of different speed participation polyreactions, and but cross-linking monomer has many addition polymerization unsaturated groups, and all back these groups are all almost participated in polyreaction with identical speed.
3. composition as claimed in claim 2, it is characterized in that described multiphase polymer is the three-phase composition, the content of described first phase (A) is 10-40 weight %, the content of second intermediate phase (B) is 45-70 weight %, the content of last phase (C) is 10-50 weight %, and all percentage ratio is all in the three-phase total polymer weight.
4. composition as claimed in claim 2, it is characterized in that described multiphase polymer is the three-phase composition, the content of described first phase (A) is 10-20 weight %, the content of second intermediate phase (B) is 50-60 weight %, the content of last phase (C) is 20-40 weight %, and all percentage ratio is all in the three-phase total polymer weight.
5. stripper plate or body by the resins of claim 1.
6. co-extrusion ejecting plate or body, wherein at least one layer comprises the resin of claim 1.
7. co-extrusion pressing plate as claimed in claim 6 or body is characterized in that other layer is selected from (methyl) acrylic polymers and multipolymer, polycarbonate, polyester and multipolymer, vinyl polymer and multipolymer, styrene polymer and multipolymer.
8. as co-extrusion pressing plate or body as described in the claim 7, it is characterized in that described resin is used in outer mulch as anti-weather.
9. matrixes for embossing by the resins of claim 1.
10. film of making by the resin of claim 1.
11. multilayer film of making by the resin of claim 1.
12. the purposes of the film of claim 10 in in-mold decoration.
13. the rete of claim 10 is pressed onto on plasticity plate or the body.
14. the film of claim 10 is as the purposes of protective layer in signal or the reflecrtive mark.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36935902P | 2002-04-02 | 2002-04-02 | |
| US60/369,359 | 2002-04-02 | ||
| US10/395643 | 2003-03-24 | ||
| US10/395,643 | 2003-03-24 |
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| CN1450117A true CN1450117A (en) | 2003-10-22 |
| CN100363420C CN100363420C (en) | 2008-01-23 |
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| CNB031103022A Expired - Lifetime CN100363420C (en) | 2002-04-02 | 2003-04-02 | Weatherable impact-resisting acrylic compositions |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI468457B (en) * | 2011-11-23 | 2015-01-11 | Lg Hausys Ltd | Acrylic resin film with excellent transparency and impact resistance and method of fabricating the same |
| CN108504061A (en) * | 2017-02-28 | 2018-09-07 | 汉达精密电子(昆山)有限公司 | Low-temperature impact-resistant PC/ABS composite materials and products thereof |
| CN114174417A (en) * | 2019-03-25 | 2022-03-11 | 盛禧奥欧洲有限责任公司 | Highly effective impact modifiers and polymer compositions |
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| JPS5427383B2 (en) * | 1973-06-16 | 1979-09-10 | ||
| FR2796648B1 (en) * | 1999-07-19 | 2002-02-01 | Atofina | COMPOSITIONS BASED ON THERMOPLASTIC METHACRYLIC (CO) POLYMER AND SHAPED ARTICLES OBTAINED FROM THESE COMPOSITIONS |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI468457B (en) * | 2011-11-23 | 2015-01-11 | Lg Hausys Ltd | Acrylic resin film with excellent transparency and impact resistance and method of fabricating the same |
| US9206294B2 (en) | 2011-11-23 | 2015-12-08 | Lg Hausys, Ltd. | Acrylic resin film having good transparency and impact resistance and method for manufacturing same |
| CN108504061A (en) * | 2017-02-28 | 2018-09-07 | 汉达精密电子(昆山)有限公司 | Low-temperature impact-resistant PC/ABS composite materials and products thereof |
| CN114174417A (en) * | 2019-03-25 | 2022-03-11 | 盛禧奥欧洲有限责任公司 | Highly effective impact modifiers and polymer compositions |
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