DE4125477A1 - Polyvinyl halide resin compsns. - contg. two-stages emulsion polymer with methyl methacrylate, alkyl:acrylate and comonomer(s), used as processing aids giving reduce gel time - Google Patents
Polyvinyl halide resin compsns. - contg. two-stages emulsion polymer with methyl methacrylate, alkyl:acrylate and comonomer(s), used as processing aids giving reduce gel timeInfo
- Publication number
- DE4125477A1 DE4125477A1 DE4125477A DE4125477A DE4125477A1 DE 4125477 A1 DE4125477 A1 DE 4125477A1 DE 4125477 A DE4125477 A DE 4125477A DE 4125477 A DE4125477 A DE 4125477A DE 4125477 A1 DE4125477 A1 DE 4125477A1
- Authority
- DE
- Germany
- Prior art keywords
- weight
- polyvinyl halide
- stage
- methyl methacrylate
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001291 polyvinyl halide Polymers 0.000 title claims abstract description 25
- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims abstract description 6
- 229920005989 resin Polymers 0.000 title abstract description 9
- 239000011347 resin Substances 0.000 title abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract 3
- 125000000217 alkyl group Chemical group 0.000 title 1
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000011342 resin composition Substances 0.000 claims description 13
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VWXLCWNPSOUPPE-UHFFFAOYSA-N (1-amino-2-methylpropylidene)azanium;chloride Chemical compound Cl.CC(C)C(N)=N VWXLCWNPSOUPPE-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
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical class CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Die Erfindung betrifft Polyvinylhalogenidharzmassen, enthaltend 0,1 bis 20 Gew.-%, bezogen auf die Menge des Polyvinylhalogenids, eines zweistufi gen Emulsionspolymerisats ausThe invention relates to polyvinyl halide resin compositions containing 0.1 to 20 wt .-%, based on the amount of polyvinyl halide, a two-stage gene emulsion polymer
50 bis 80 Gew.-% einer 1. Stufe aus
80 bis 99,5 Gew.-% Methylmethacrylat,
0,5 bis 9,9 Gew.-% eines C₁-C₁₈-Alkylacrylats und
0 bis 10,1 Gew.-% weiterer Comonomere,
und50 to 80 wt .-% of a 1st stage
80 to 99.5% by weight of methyl methacrylate,
0.5 to 9.9 wt .-% of a C₁-C₁₈ alkyl acrylate and
0 to 10.1% by weight of further comonomers, and
20 bis 50 Gew.-% einer 2. Stufe aus
70 bis 90 Gew.-% Methylmethacrylat,
10 bis 30 Gew.-% eines C₁-C₁₈-Alkylacrylats und
0 bis 20 Gew.-% weiterer Comonomere.20 to 50 wt .-% of a second stage
70 to 90% by weight of methyl methacrylate,
10 to 30 wt .-% of a C₁-C₁₈ alkyl acrylate and
0 to 20% by weight of other comonomers.
Weiterhin betrifft die Erfindung die Verwendung des zweistufigen Emul sionspolymerisats als Verarbeitungshilfsmittel in Polyvinylhalogenid harzmassen.The invention further relates to the use of the two-stage emul sion polymer as processing aid in polyvinyl halide resin masses.
Bei der Verarbeitung von Polyvinylhalogenidharzmassen, insbesondere von Polyvinylchloridharzmassen, zu Formteilen sind kurze Gelier- und Plastifi zierzeiten der Harzmassen besonders wünschenswert, da die Verarbeitungs temperaturen nahe an der Zersetzungstemperatur des Polyvinylhalogenids liegen.When processing polyvinyl halide resin compositions, in particular Polyvinylchloride resin masses to form parts are short gelling and plastifi Decoration times of the resin masses are particularly desirable because of the processing temperatures close to the decomposition temperature of the polyvinyl halide lie.
Um die Gelierungs- und Plastifizierungszeiten von Polyvinylchloridharz massen zu verkürzen, werden den Harzmassen Verarbeitungshilfsmittel zugesetzt, z. B. Copolymere des Methylmethacrylats mit Alkylacrylaten (DE-A-21 26 924 und DE-A-21 01 808) .The gelation and plasticization times of polyvinyl chloride resin Shortening the masses, the resin masses are processing aids added, e.g. B. Copolymers of methyl methacrylate with alkyl acrylates (DE-A-21 26 924 and DE-A-21 01 808).
Aus der DE-A-22 13 214 sind Pfropfpolymerisate aus 50 bis 99 Gew.-% einer Pfropfgrundlage aus überwiegend Methylmethacrylat und 1 bis 50 Gew.-% einer Pfropfhülle aus überwiegend Acrylsäureestern bekannt.From DE-A-22 13 214 graft polymers of 50 to 99% by weight are one Graft base consisting predominantly of methyl methacrylate and 1 to 50% by weight a graft made from predominantly acrylic acid esters.
In der DE-A-23 63 564 sind Pfropfpolymerisate aus 1 bis 49 Gew.-% einer Pfropfgrundlage aus vorwiegend Methylmethacrylat und 51 bis 99 Gew.-% einer Pfropfhülle, welche neben Methylmethacrylat 10 bis 45 Gew.-% eines Acrylsäureesters enthält, beschrieben.In DE-A-23 63 564, graft polymers of 1 to 49% by weight are one Graft base consisting primarily of methyl methacrylate and 51 to 99% by weight a graft which, in addition to methyl methacrylate, contains 10 to 45% by weight of a Contains acrylic acid ester described.
Die bisher bekannten Verarbeitungshilfsmittel vermögen jedoch hinsichtlich der Gelier- und Plastifizierzeiten nicht ganz zu befriedigen.The processing aids known to date, however, are capable of the gelling and plasticizing times are not entirely satisfactory.
Aufgabe der vorliegenden Erfindung war es, diesem Mangel abzuhelfen.The object of the present invention was to remedy this deficiency.
Demgemäß wurden die eingangs definierten Polyvinylhalogenidharzmassen gefunden.Accordingly, the polyvinyl halide resin compositions defined at the outset found.
Vorzugsweise enthalten die Polyvinylhalogenidharzmassen 1 bis 10 Gew.-% insbesondere 1 bis 7 Gew.-% bezogen auf die Menge des Polyvinylhalogenids des zweistufigen Emulsionspolymerisats.The polyvinyl halide resin compositions preferably contain 1 to 10% by weight. in particular 1 to 7 wt .-% based on the amount of polyvinyl halide of the two-stage emulsion polymer.
Der Gewichtsanteil des C1-C18-Alkylacrylats in der 2. Stufe ist bevorzugt mindestens 5, besonders bevorzugt mindestens 10, Gewichtsprozent größer als in der 1. Stufe.The weight fraction of the C 1 -C 18 -alkyl acrylate in the second stage is preferably at least 5, particularly preferably at least 10, percent by weight greater than in the first stage.
Das Emulsionspolymerisat besteht bevorzugt ausThe emulsion polymer preferably consists of
60 bis 80 Gew.-% der 1. Stufe,
20 bis 40 Gew.-% der 2. Stufe.60 to 80% by weight of the 1st stage,
20 to 40% by weight of the second stage.
Die 1. Stufe besteht bevorzugt aus
90,1 bis 95 Gew.-% Methylmethacrylat und
5 bis 9,9 Gew.-% eines C₁-C₁₈-Alkylacrylats undThe 1st stage preferably consists of
90.1 to 95 wt .-% methyl methacrylate and
5 to 9.9 wt .-% of a C₁-C₁₈ alkyl acrylate and
die 2. Stufe besteht bevorzugt aus
70 bis 80 Gew.-% Methylmethacrylat und
20 bis 30 Gew.-% eines C₁-C₁₈-Alkylacrylats.the second stage preferably consists of
70 to 80 wt .-% methyl methacrylate and
20 to 30 wt .-% of a C₁-C₁₈ alkyl acrylate.
Bei den C1-C18-Alkylacrylaten handelt es sich bevorzugt um Methylacrylat, Ethylacrylat, n-Propylacrylat, n-Butylacrylat oder 2-Ethylhexylacrylat.The C 1 -C 18 -alkyl acrylates are preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate.
In der 1. Stufe sind C1 bis C6, insbesondere C1 bis C4 Alkylacrylate bevorzugt. In der 2. Stufe sind C4 bis C18, insbesondere C6 bis C18 Alkyl acrylate bevorzugt.In the 1st stage, C 1 to C 6 , in particular C 1 to C 4, alkyl acrylates are preferred. In the second stage, C 4 to C 18 , in particular C 6 to C 18 alkyl acrylates are preferred.
Als weitere Comonomere kommen bevorzugt Styrol, α-Methylstyrol, Acryl nitril, Methacrylnitril, Vinylester, wie Vinylacetat und Vinylpropionat sowie C2-C10-Alkylmethacrylate in Betracht. Other preferred comonomers are styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl esters, such as vinyl acetate and vinyl propionate, and C 2 -C 10 -alkyl methacrylates.
Die Herstellung des zweistufigen Polymerisats erfolgt durch Emulsions polymerisation in an sich bekannter Weise.The two-stage polymer is prepared by emulsions polymerization in a manner known per se.
Als Emulgatoren können z. B. Alkalisalze von längerkettigen Fettsäuren, Alkylsulfate, Alkylsulfonate, alkylierte Arylsulfonate oder alkylierte Biphenylethersulfonate, Salze der Abietinsäure oder deren Derivate sowie Sulfobernsteinsäureester verwendet werden.As emulsifiers, for. B. alkali salts of longer-chain fatty acids, Alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated Biphenyl ether sulfonates, salts of abietic acid or their derivatives and Sulfosuccinic acid esters can be used.
Geeignete Initiatoren sind z. B. Natrium-, Kalium- und Ammoniumpersulfat, tert.-Butylhydroperoxid, wasserlösliche Azoverbindungen sowie die Salze der 4,4′-Azobis[4-cyanopentansäure] oder 2,2′-Azobis[2-amidinopropan hydrochlorid]. Für die Polymerisation bei relativ niedriger Temperatur eignen sich insbesondere Redoxsysteme aus einem Persulfat oder einem Hydroperoxid sowie einem Reduktionsmittel in Verbindung mit einem Eisen (II)-Salz. Geeignete Reduktionsmittel sind beispielsweise Natrium-meta bisulfit, Natriumhydroxymethansulfinat und Ascorbinsäure.Suitable initiators are e.g. B. sodium, potassium and ammonium persulfate, tert-butyl hydroperoxide, water-soluble azo compounds and the salts 4,4′-azobis [4-cyanopentanoic acid] or 2,2′-azobis [2-amidinopropane hydrochloride]. For polymerization at a relatively low temperature Redox systems made from a persulfate or a are particularly suitable Hydroperoxide and a reducing agent combined with an iron (II) salt. Suitable reducing agents are, for example, sodium meta bisulfite, sodium hydroxymethanesulfinate and ascorbic acid.
Die Emulsionspolymerisation wird vorzugsweise bei Temperaturen zwischen 30 und 95°C durchgeführt.The emulsion polymerization is preferably carried out at temperatures between 30 and 95 ° C performed.
Durch die Polymerisationstemperatur wird im wesentlichen das Molekular gewicht des gebildeten Polymeren beeinflußt, d. h. je höher die Temperatur, desto niedriger das Molekulargewicht. Die Polymerisationstemperatur kann bei beiden Stufen des Polymerisates gleich oder unterschiedlich sein. Zur Charakterisierung der Molekülgröße dient in der Regel eine Viskositäts messung. Eine gebräuchliche Größe ist der K-Wert nach Fikentscher. In 1%ger Lösung in Tetrahydrofuran kann der K-Wert der beanspruchten Poly merisate zwischen 80 und 150 betragen. Bevorzugt liegt er zwischen 90 und 130, besonders bevorzugt zwischen 100 und 120.The polymerization temperature essentially makes the molecular affects the weight of the polymer formed, d. H. the higher the temperature, the lower the molecular weight. The polymerization temperature can be the same or different in both stages of the polymer. To Characterization of the molecular size usually serves a viscosity Measurement. A common parameter is the Fikentscher K value. In 1% solution in tetrahydrofuran can have the K value of the claimed poly merisates between 80 and 150. It is preferably between 90 and 130, particularly preferably between 100 and 120.
Zunächst werden die Monomeren der 1. Stufe polymerisiert. Die Monomeren der 1. Stufe werden bevorzugt zu mehr als 95 Gew.-% insbesondere zu mehr als 99 Gew.-% auspolymerisiert, bevor mit der Zugabe der Monomeren der 2. Stufe begonnen wird.First, the first stage monomers are polymerized. The monomers the 1st stage is preferably more than 95% by weight, in particular more polymerized as 99 wt .-% before with the addition of the monomers 2nd stage is started.
Die Teilchengröße der Emulsionspolymerisate kann durch die Wahl der Polymerisationsbedingungen eingestellt werden, wie es z. B. in der DE-C 22 30 989 beschrieben ist. Die Teilchengröße hängt z. B. von der Rührergeschwindigkeit ab. Bevorzugt sind mittlere Teilchendurchmesser d50 (Volumenmittel) zwischen ca. 50 und 300 nm.The particle size of the emulsion polymers can be adjusted by the choice of the polymerization conditions, such as. B. is described in DE-C 22 30 989. The particle size depends e.g. B. from the stirrer speed. Average particle diameters d 50 (volume average) between approximately 50 and 300 nm are preferred.
Der Feststoffgehalt der Emulsionen beträgt bevorzugt 30 bis 60 Gew.-%. Das Polymerisat kann aus der Emulsion durch Fällung und anschließende Trock nung oder in einem Verfahrensschritt durch Sprühtrocknung als weitgehend wasserfreies Pulver isoliert werden.The solids content of the emulsions is preferably 30 to 60% by weight. The Polymer can be removed from the emulsion by precipitation and subsequent drying tion or in one process step by spray drying as largely anhydrous powder can be isolated.
Die Sprühtrocknung kann in bekannter Weise durchgeführt werden, wie es z. B. im "Spray drying handbook" (K. Mosters, New York 1985) beschrieben ist. Die Eintrittstemperatur des Trockengases in den Sprühturm liegt zweckmäßigerweise zwischen 100 und 200°C und die Temperatur des getrock neten Pulvers am Ausgang des Sprühturms beträgt bevorzugt 40 bis 100°C.Spray drying can be carried out in a known manner as it is e.g. B. in the "Spray drying handbook" (K. Mosters, New York 1985) is. The inlet temperature of the dry gas in the spray tower is expediently between 100 and 200 ° C and the temperature of the dried Neten powder at the outlet of the spray tower is preferably 40 to 100 ° C.
Man erhält rieselfähige Pulver, deren mittlerer Teilchendurchmesser im allgemeinen 50 bis 500 µm, insbesondere 100 bis 300 µm beträgt.Free-flowing powders are obtained, whose average particle diameter is in the is generally 50 to 500 microns, especially 100 to 300 microns.
Besonders gut verarbeitbare Pulver mit guter Rieselfähigkeit und geringen Verbackungseigenschaften erhält man, wenn die Erweichungstemperatur (Vicat B, bestimmt nach DIN 53 460) oberhalb von 80°C liegt. Zweckmäßiger weise sollte daher der Gesamtgehalt an C1-C18 Alkylacrylat im zweistufigen Emulsionspolymerisat 15 Gew.-% nicht übersteigen. Bei einem höheren Anteil des C1-C18 Alkylacrylats wird die Erweichungstemperatur in unerwünschtem Ausmaß erniedrigt.Powders that are particularly easy to process with good flow properties and low caking properties are obtained if the softening temperature (Vicat B, determined according to DIN 53 460) is above 80 ° C. The total content of C 1 -C 18 alkyl acrylate in the two-stage emulsion polymer should therefore expediently not exceed 15% by weight. With a higher proportion of the C 1 -C 18 alkyl acrylate, the softening temperature is lowered to an undesirable extent.
Beim Polyvinylhalogenid in der erfindungsgemäßen Polyvinylhalogenidharz masse kann es sich insbesondere um Homopolymere des Vinylchlorids, um Copolymere des Vinylchlorids mit mindestens 80 Gew.-% Vinylchlorid oder um nachchloriertes Polyvinylchlorid handeln. Bevorzugt handelt es sich um Homopolymere des Vinylchlorids (Polyvinylchlorid).In the case of polyvinyl halide in the polyvinyl halide resin according to the invention mass can be, in particular, homopolymers of vinyl chloride Copolymers of vinyl chloride with at least 80% by weight vinyl chloride or um post-chlorinated polyvinyl chloride. It is preferably about Homopolymers of vinyl chloride (polyvinyl chloride).
Die erfindungsgemäßen Polyvinylhalogenidharzmassen können neben dem Emulsionspolymerisat und dem Polyvinylhalogenid weitere Zusatzstoffe, z. B. Modifizierungsmittel zur Verbesserung der Schlagzähigkeit, Wärmeformbe ständigkeit und Witterungsbeständigkeit, sowie Stabilisatoren, Gleit mittel, Füllstoffe, Farbstoffe und Pigmente enthalten. Im allgemeinen liegt die Gesamtmenge der weiteren Zusatzstoffe unter 40, insbesondere unter 30 Gew.-% bezogen auf die Menge des Polyvinylhalogenids.The polyvinyl halide resin compositions according to the invention can in addition to the Emulsion polymer and the polyvinyl halide other additives, for. B. Modifiers to improve impact resistance, heat molding resistance and weather resistance, as well as stabilizers, sliding medium, fillers, dyes and pigments. In general the total amount of further additives is below 40, in particular below 30 wt .-% based on the amount of polyvinyl halide.
Die Herstellung der erfindungsgemäßen Polyvinylhalogenidharzmassen kann durch Abmischen der pulverförmigen zweistufigen Emulsionspolymerisate mit einem Polyvinylhalogenid und gegebenenfalls weiteren Zusatzstoffen nach üblichen Methoden, z. B. in einem Extruder, Kneter oder einer Walze er folgen.The production of the polyvinyl halide resin compositions according to the invention can by mixing the powdery two-stage emulsion polymers with a polyvinyl halide and optionally other additives usual methods, e.g. B. in an extruder, kneader or a roller consequences.
Die Polyvinylhalogenidharzmasse kann durch für Thermoplaste übliche Methoden (Extrudieren, Spritzgießen, Kalandrieren, Pressen, Tiefziehen u. ä.) in die gewünschte Form gebracht werden. The polyvinyl halide resin composition can be made by the usual for thermoplastics Methods (extrusion, injection molding, calendering, pressing, deep drawing u. Ä.) are brought into the desired shape.
Die erfindungsgemäßen Polyvinylhalogenidharzmassen zeichnen sich durch kurze Gelier- und Plastifizierzeiten aus. Durch kurze Gelier- und Plasti fizierzeiten wird eine schnellere und damit wirtschaftlichere Verarbeitung ermöglicht.The polyvinyl halide resin compositions according to the invention are notable for short gelling and plasticizing times. With short gelling and plasti processing times will be faster and therefore more economical processing enables.
Dieses Polymerisat wurde unter Verwendung der folgenden Ausgangsmischungen hergestelltThis polymer was prepared using the following starting mixtures produced
Vorlage:
2200 g Wasser
0,032 g Eisen(II)-sulfat Heptahydrat
6,4 g Tetranatriumpyrophosphat
3,2 g Laurinsäure
2,56 g 25-%ige Natronlauge
3,2 g NatriumpersulfatTemplate:
2200 g water
0.032 g iron (II) sulfate heptahydrate
6.4 g tetrasodium pyrophosphate
3.2 g lauric acid
2.56 g of 25% sodium hydroxide solution
3.2 g sodium persulfate
Zulauf 1:
2430 g Wasser
32 g Laurinsäure
25,6 g 25-%ige Natronlauge
1560 g Methylmethacrylat
40 g MethylacrylatInlet 1:
2430 g water
32 g lauric acid
25.6 g 25% sodium hydroxide solution
1560 g methyl methacrylate
40 g methyl acrylate
Zulauf 2:
500 g Wasser
3,2 g Natriummetabisulfit
3,2 g 25-%ige NatronlaugeInlet 2:
500 g water
3.2 g sodium metabisulfite
3.2 g 25% sodium hydroxide solution
Zulauf 3:
50 g Wasser
3,2 g NatriumpersulfatInlet 3:
50 g water
3.2 g sodium persulfate
Zulauf 4:
1280 g Methylmethacrylat
320 g Butylacrylat.Inlet 4:
1280 g methyl methacrylate
320 g butyl acrylate.
Zur Vorlage wurden unter Rühren 272 g der Zulaufmischung 1 gegeben und das Gemisch wurde auf 60°C erwärmt. Bei dieser Temperatur wurden der Rest von Zulaufmischung 1 und 40% von Zulauf 2 in 2 h gleichmäßig zudosiert und noch 1 h bei 60°C gerührt. Anschließend wurde Zulauf 3 auf einmal zuge geben und dann Zulauf 4 in 2 h zudosiert. Beginnend mit Zulauf 4 wurden die restlichen 60% von Zulauf 2 innerhalb von 3 h zudosiert. Die erhal tenen Dispersion wies einen Feststoffgehalt von 37,6 Gew.-% und einen pH-Wert von 9,1 auf.For stirring, 272 g of feed mixture 1 were added and the The mixture was heated to 60 ° C. At this temperature the rest of Feed mixture 1 and 40% of feed 2 evenly metered in over 2 h and stirred at 60 ° C for 1 h. Feed 3 was then drawn in at once give and then feed 4 metered in 2 h. Starting with inlet 4 were the remaining 60% of feed 2 were metered in within 3 h. The receive The dispersion had a solids content of 37.6% by weight and a pH of 9.1.
Die Emulsionspolymerisate B bis G und die Vergleichspolymerisate a und b wurden in entsprechender Weise hergestellt.The emulsion polymers B to G and the comparison polymers a and b were produced in a corresponding manner.
Die Zusammensetzung der Emulsionspolymerisate ist in Tabelle 1 angegeben. Die Erweichungstemperaturen (Vicat B, DIN 53 460) und der Gesamtgehalt an Alkylacrylat im zweistufigen Emulsionspolymerisat sind in Tabelle 2 aufge listet. The composition of the emulsion polymers is given in Table 1. The softening temperatures (Vicat B, DIN 53 460) and the total content Alkyl acrylate in the two-stage emulsion polymer are listed in Table 2 lists.
In einem Heißmischer wurde zunächst bei 120°C eine Grundmischung aus
100 Gew.-Teilen eines Suspensions-Polyvinylchlorid (K-Wert 68)
1 Gew.-Teil tribasisches Bleisulfat
0,3 Gew.-Teile Bleistearat
0,6 Gew.-Teile C₁₆/C₁₈ Fettalkohol und
0,1 Gew.-Teile Calciumstearat hergestellt und
die Prüfung des Verarbeitungsverhaltens erfolgte in einem Brabender-
Plasticorder mit Walzenkneter (Typ W 30 H) mit einem Knetkammervolumen von
30 cm3. Es wurden jeweils 31 g Mischung eingesetzt, die im Falle von
2 Gew.-% Zusatz des Emulsionspolymerisats durch Untermischen von 0,6 g
Emulsionspolymerisat in 30,4 g Grundmischung, im Falle von 5 Gew.-% Zusatz
durch Untermischen von 1,5 g Emulsionspolymerisat in 29,5 g Grundmischung
hergestellt wurden.In a hot mixer, a basic mixture was first made at 120 ° C
100 parts by weight of a suspension polyvinyl chloride (K value 68)
1 part by weight of tribasic lead sulfate
0.3 parts by weight of lead stearate
0.6 parts by weight of C₁₆ / C₁₈ fatty alcohol and
0.1 parts by weight of calcium stearate produced and
The processing behavior was tested in a Brabender plasticorder with a roller kneader (type W 30 H) with a kneading chamber volume of 30 cm 3 . In each case 31 g of mixture were used, which in the case of 2% by weight addition of the emulsion polymer by mixing in 0.6 g of the emulsion polymer in 30.4 g basic mixture, in the case of 5% by weight addition by mixing in 1.5 g emulsion polymer were prepared in 29.5 g basic mixture.
Geprüft wurde das Verarbeitungsverhalten bei 170°C und einer Drehzahl von 40 Upm der rechtsdrehenden Schaufel. Das Drehzahlverhältnis der links- und rechtsdrehenden Kneterschaufeln betrug 1,5 : 1.The processing behavior at 170 ° C and a speed of 40 rpm of the right-turning blade. The speed ratio of the left and right-hand kneader blades was 1.5: 1.
Mit Hilfe eines Schreibers wurde der Verlauf des Drehmomentes während der Versuche aufgezeichnet und aus den Kurven die Gelierzeiten und die Plastifizierzeiten, welche als Minimum bzw. Maximum der Kurve definiert sind, entnommen (s. Tabelle 3). With the help of a recorder, the course of the torque during the Experiments recorded and the gel times and the Plasticizing times, which are defined as the minimum or maximum of the curve are taken (see Table 3).
Claims (3)
50 bis 80 Gew.-% einer 1. Stufe aus
80 bis 99,5 Gew.-% Methylmethacrylat,
0,5 bis 9,9 Gew.-% eines C₁-C₁₈-Alkylacrylats und
0 bis 10,1 Gew.-% weiterer Comonomere und 20 bis 50 Gew.-% einer 2. Stufe aus
70 bis 90 Gew-% Methylmethacrylat,
10 bis 30 Gew.-% eines C₁-C₁₈-Alkylacrylats und
0 bis 20 Gew.-% weiterer Comonomere.1. Polyvinyl halide resin compositions containing 0.1 to 20% by weight, based on the amount of polyvinyl halide, of a two-stage emulsion polymer
50 to 80 wt .-% of a 1st stage
80 to 99.5% by weight of methyl methacrylate,
0.5 to 9.9 wt .-% of a C₁-C₁₈ alkyl acrylate and
0 to 10.1% by weight of further comonomers and 20 to 50% by weight of a second stage
70 to 90% by weight methyl methacrylate,
10 to 30 wt .-% of a C₁-C₁₈ alkyl acrylate and
0 to 20% by weight of other comonomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4125477A DE4125477B4 (en) | 1990-08-10 | 1991-08-01 | Polyvinyl halide resin composition with improved processing behavior, their use and use of an emulsion polymer as a processing aid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4025362.7 | 1990-08-10 | ||
| DE4025362 | 1990-08-10 | ||
| DE4125477A DE4125477B4 (en) | 1990-08-10 | 1991-08-01 | Polyvinyl halide resin composition with improved processing behavior, their use and use of an emulsion polymer as a processing aid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE4125477A1 true DE4125477A1 (en) | 1992-02-13 |
| DE4125477B4 DE4125477B4 (en) | 2004-02-12 |
Family
ID=30124440
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE4125477A Expired - Lifetime DE4125477B4 (en) | 1990-08-10 | 1991-08-01 | Polyvinyl halide resin composition with improved processing behavior, their use and use of an emulsion polymer as a processing aid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4425625C1 (en) * | 1994-07-20 | 1996-01-04 | Degussa | Process for the preparation of unglazed, low-monomer homo- or copolymers of methyl methacrylate, an emulsion polymer of polymethyl methacrylate obtainable by this process with a comonomer content of less than 5% by weight and the use of the emulsion polymer |
| WO2013100997A1 (en) * | 2011-12-28 | 2013-07-04 | Rohm And Haas Company | Processing aids and polymer formulations containing the same and method for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT960769B (en) * | 1971-03-16 | 1973-11-30 | Kanegafuchi Chemical Ind | COMPOSITIONS OF VINYLCLO RURO RESIN |
| CA1038534A (en) * | 1972-12-29 | 1978-09-12 | Mitsubishi Rayon Company Ltd. | Vinyl chloride polymer composition |
-
1991
- 1991-08-01 DE DE4125477A patent/DE4125477B4/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4425625C1 (en) * | 1994-07-20 | 1996-01-04 | Degussa | Process for the preparation of unglazed, low-monomer homo- or copolymers of methyl methacrylate, an emulsion polymer of polymethyl methacrylate obtainable by this process with a comonomer content of less than 5% by weight and the use of the emulsion polymer |
| EP0693501A1 (en) | 1994-07-20 | 1996-01-24 | Degussa Ag | Process for preparing non vitrified, low residual monomers containing processing aids for thermoplastic polymers, thereby obtainable processing aids and their uses |
| WO2013100997A1 (en) * | 2011-12-28 | 2013-07-04 | Rohm And Haas Company | Processing aids and polymer formulations containing the same and method for producing the same |
| US9908958B2 (en) | 2011-12-28 | 2018-03-06 | Rohm And Haas Company | Processing aids and polymer formulations containing the same and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4125477B4 (en) | 2004-02-12 |
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