DE1103585B - Process for the production of acrylic and methacrylic acid polymers and copolymers - Google Patents
Process for the production of acrylic and methacrylic acid polymers and copolymersInfo
- Publication number
- DE1103585B DE1103585B DEG22766A DEG0022766A DE1103585B DE 1103585 B DE1103585 B DE 1103585B DE G22766 A DEG22766 A DE G22766A DE G0022766 A DEG0022766 A DE G0022766A DE 1103585 B DE1103585 B DE 1103585B
- Authority
- DE
- Germany
- Prior art keywords
- acrylic
- crosslinking agent
- methacrylic acid
- copolymers
- production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 12
- 229920000642 polymer Polymers 0.000 title claims description 12
- 229920001577 copolymer Polymers 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- YFDGKIUMYANSBZ-UHFFFAOYSA-N 1-[1,3-di(prop-2-enoyl)-2,4-dihydrotriazin-5-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CC(C(=O)C=C)=CN(C(=O)C=C)N1 YFDGKIUMYANSBZ-UHFFFAOYSA-N 0.000 claims description 4
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical compound NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 claims description 4
- KDAMTBXGNYFCMP-UHFFFAOYSA-N 1-[1,3-bis(2-methylprop-2-enoyl)-2,4-dihydrotriazin-5-yl]-2-methylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CC(C(=O)C(C)=C)=CN(C(=O)C(C)=C)N1 KDAMTBXGNYFCMP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- NALBLJLOBICXRH-UHFFFAOYSA-N dinitrogen monohydride Chemical group N=[N] NALBLJLOBICXRH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- -1 acrylyl Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DNVUITIVPMGLBU-UHFFFAOYSA-N 1,3,5-trithiane 1,1,3,3,5,5-hexaoxide Chemical compound O=S1(=O)CS(=O)(=O)CS(=O)(=O)C1 DNVUITIVPMGLBU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical class OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical class CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SWYBJLRZPSNABC-UHFFFAOYSA-N 3-prop-2-enoyloxyprop-2-enoic acid Chemical compound OC(=O)C=COC(=O)C=C SWYBJLRZPSNABC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IYFLKRVTVNYTLE-UHFFFAOYSA-N CC(=O)C=C.C(CCC)OC=C Chemical compound CC(=O)C=C.C(CCC)OC=C IYFLKRVTVNYTLE-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 239000012897 dilution medium Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- FEZFGASTIQVZSC-UHFFFAOYSA-N nonanoyl nonaneperoxoate Chemical compound CCCCCCCCC(=O)OOC(=O)CCCCCCCC FEZFGASTIQVZSC-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-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
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- SPDUKHLMYVCLOA-UHFFFAOYSA-M sodium;ethaneperoxoate Chemical compound [Na+].CC(=O)O[O-] SPDUKHLMYVCLOA-UHFFFAOYSA-M 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F28/00—Homopolymers and 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 bond to sulfur or by a heterocyclic ring containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
Verfahren zur Herstellung von Acryl-und Methacrylsäurepolymerisaten und-mischpolymerisaten Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuartiger Polymerisate und Mischpolymerisate der Acryl-und Methacrylsäure. Process for the production of acrylic and methacrylic acid polymers and copolymers The present invention relates to a process for the preparation new types of polymers and copolymers of acrylic and methacrylic acid.
Es ist bereits bekannt, daß durch Kondensation von Acrylsäurenitril mit Formaldehyd erhaltene Verbindungen bei der Herstellung von Polymerisaten aus polymerisierbaren Estern verwendet werden können. It is already known that by condensation of acrylonitrile compounds obtained with formaldehyde in the production of polymers polymerizable esters can be used.
Die auf diese Weise hergestellten Polymerisate ergeben jedoch in alkalischen Systemen keine stark quellenden Massen, wie sie für verschiedene technische Zwecke benötigt werden, da man bei der zur Herstellung derartiger Produkte notwendigen Hydrolyse auch die vernetzenden Bindungen zerstören würde. Wenn man hingegen-der vorliegenden Erfindung folgend-Acrylsäuren mit einem derartigen Vernetzungsmittel, wie 1, 3, 5-Triacryltriazin, umsetzt, so erhält man die erwünschten stark quellenden, aber dennoch unlöslichen Polymerisate.The polymers produced in this way, however, result in alkaline Systems do not have strongly swelling masses, as they are for various technical purposes are needed, as one is necessary in the manufacture of such products Hydrolysis would also destroy the crosslinking bonds. On the other hand, if you-the following the present invention-acrylic acids with such a crosslinking agent, such as 1, 3, 5-triacryltriazine, reacted, the desired strongly swelling, but still insoluble polymers.
Erfindungsgemäß wird dementsprechend ein Verfahren zur Herstellung von Acryl-und Methacrylsäurepolymerisaten und-mischpolymerisaten vorgeschlagen, bei dem Acryl-oder Methacrylsäure, gegebenenfalls zusammen mit einem oder mehreren weiteren mischpolymerisierbaren Monomeren, in Gegenwart einer geringen Menge eines Vernetzungsmittels, das zwei oder mehrere CH, = C---Gruppen und 2 oder 3 Amino-oder Imino-Stickstoffatome oder 3 sauerstofftragende Schwefelatome im Molekül enthält, polymerisiert wird. According to the invention there is accordingly a method of production proposed by acrylic and methacrylic acid polymers and copolymers, in the case of acrylic or methacrylic acid, optionally together with one or more further copolymerizable monomers, in the presence of a small amount of one Crosslinking agent containing two or more CH, = C --- groups and 2 or 3 amino or Contains imino nitrogen atoms or 3 oxygen-carrying sulfur atoms in the molecule, is polymerized.
Die bei der Durchführung des Verfahrens der vorliegenden Erfindung erhaltenen Polymerisate und Mischpolymerisate können z. B. nach Umwandlung in die entsprechenden Partialester-oder Partialamidderivate als Suspendiermittel in schleimartigen Zubereitungen verwendet werden. Diese Zubereitungen erhalten hierdurch eine gute Beständigkeit. Those used in carrying out the method of the present invention obtained polymers and copolymers can, for. B. after conversion to the corresponding partial ester or partial amide derivatives as suspending agents in slimy Preparations are used. This gives these preparations a good one Resistance.
Die bevorzugten Vernetzungsmittel enthalten zwei oder mehrere Acrylyl-oder Allylgruppen. Besonders geeignete Vernetzungsmittel dieser Art sind Methylenbis-acrylsäureamide, Polyacrylyltriazine, z. B. 1, 3, 5-Triacrylyltriazin, Polymethacrylyltriazine, z. B. 1, 3, 5-Trimethacrylyltriazin, Polyallyltrimethylentrisulfone, z. B. The preferred crosslinking agents contain two or more acrylyl or Allyl groups. Particularly suitable crosslinking agents of this type are methylenebisacrylic acid amides, Polyacrylyl triazines, e.g. B. 1, 3, 5-triacrylyltriazine, polymethacrylyltriazines, e.g. B. 1, 3, 5-trimethacrylyltriazine, polyallyltrimethylene trisulfones, e.g. B.
Hexaallyltrimethylentrisulfon, und Polyallylcyanurate, z. B. Triallylcyanurat.Hexaallyl trimethylene trisulfone, and polyallyl cyanurates, e.g. B. triallyl cyanurate.
An Stelle von Acryl-oder Methacrylsäure als Monomeren kann auch eine substituierte Acryl-oder Methacrylsäure, z. B. Athacrylsäure, a-Chloracrylsäure, a-Cyanacrylsäure, 3-StyryIacryIsäure (1-Carboxy-4-phenylbutadien-1, 3), jS-Methylacrylsäure, a-Phenylacrylsäure, ß-Acryloxyacrylsäure usw. verwendet werden. Instead of acrylic or methacrylic acid as monomers, a substituted acrylic or methacrylic acid, e.g. B. Athacrylic acid, a-chloroacrylic acid, α-Cyanoacrylic acid, 3-StyryIacryI acid (1-Carboxy-4-phenylbutadiene-1, 3), jS-methylacrylic acid, α-phenylacrylic acid, β-acryloxyacrylic acid, etc. can be used.
Als Comonomere, die mit Acryl-und Methacrylsäure mischpolymerisierbar sind, können zweckmäßig monoolefinische Monomere, wie Styrol, die Chlor-und Äthoxystyrole, Acrylsäureamid, N-Methylacrylsäureamid, N, N-Dimethylacrylsäureamid, Acrylsäurenitril, Methacrylsäurenitril, Methylacrylat, Äthylacrylat, 2-Äthylhexylacrylat, Methylmethacrylat, Vinylacetat, Vinylbenzoat, Vinylpyridin, Vinylchlorid, Vinylidenchlorid, Vinylidenchlorbromid, Vinylcarbazol, Vinylpyrrolidon, Methylvinyläther, Äthylvinyläther, n-Butylvinyläther Methylvinylketon, Äthylen, Isobutylen, Dimethylmaleat und Diäthylmaleat, verwendet werden. Außer diesen Monomeren können auch Divinyl-oder Dialkenylester oder andere polyfunktionelle Ester, Amide, Äther und Ketone u. dgl. verwendet werden. As comonomers that are copolymerizable with acrylic and methacrylic acid are, can expediently monoolefinic monomers, such as styrene, the chloro- and ethoxystyrenes, Acrylic acid amide, N-methylacrylic acid amide, N, N-dimethylacrylic acid amide, acrylonitrile, Methacrylic acid nitrile, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Vinyl acetate, vinyl benzoate, vinyl pyridine, vinyl chloride, vinylidene chloride, vinylidene chlorobromide, Vinyl carbazole, vinyl pyrrolidone, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether Methyl vinyl ketone, ethylene, isobutylene, dimethyl maleate and diethyl maleate are used will. In addition to these monomers, divinyl or dialkenyl esters or others can also be used polyfunctional esters, amides, ethers and ketones and the like can be used.
Das angewandte inerte Verdünnungsmittel soll eine gewisse lösende Wirkung auf einen oder mehrere der monomeren Bestandteile, jedoch nicht auf das entstehende Polymerisat haben. Die Polymerisation kann in einem wäßrigen Medium ausgeführt werden, das einen wasserlöslichen, freie Radikale bildenden Peroxydkatalysator enthält, wobei das Produkt entweder als körniger Niederschlag oder als stark gequollenes Gel erhalten wird ; hiervon kann jedes direkt verwendet oder leicht weiter zerkleinert und getrocknet werden. Die Polymerisation in einer organischen Flüssigkeit, die ein Lösungsmittel für die Monomeren, aber nicht für das Polymerisat ist, oder in einem Gemisch solcher Lösungsmittel in Gegenwart eines losungsmittellöslichen Katalysators wird bei weitem bevorzugt, weil das Produkt gewöhnlich als sehr feiner, zerbröckelnder und häufig flockiger Niederschlag erhalten wird, der nach Abtrennen des Lösungsmittels nur selten zermahlen werden muß oder eine andere weitere Behandlung vor der Verwendung erfordert. Geeignete Lösungsmittel sind z. B. Benzol, Xylol, Tetrahydronaphthalin, Hexan, Heptan, Tetrachlorkohlenstoff, Methylchlorid, Äthylchlorid und Bromtrichlormethan und Gemische von diesen und anderen Lösungsmitteln. The inert diluent used should have a certain dissolving effect Effect on one or more of the monomeric constituents, but not on the have resulting polymer. The polymerization can be carried out in an aqueous medium run, which is a water-soluble, free radical-forming peroxide catalyst contains, the product either as a granular precipitate or as a heavily swollen Gel is obtained; Each of these can be used directly or further crushed and dried. Polymerization in an organic liquid that is a solvent for the monomers, but not for the polymer, or in a mixture of such solvents in the presence of a solvent-soluble catalyst is by far preferred because the product is usually considered to be very fine, more crumbling and often fluffy precipitate is obtained after removal of the solvent are rarely ground must or some other further treatment Requires before use. Suitable solvents are e.g. B. benzene, xylene, Tetrahydronaphthalene, hexane, heptane, carbon tetrachloride, methyl chloride, ethyl chloride and bromotrichloromethane and mixtures of these and other solvents.
Die Polymerisation in dem Verdünnungsmedium kann in Gegenwart eines freie Radikale bildenden Katalysators in einem geschlossenen Gefäß in einer inerten Atmosphäre und unter Eigendruck oder zusätzlichem Druck oder in einem offenen Gefäß unter Rückfluß bei normalem Druck durchgeführt werden. Die Temperatur kann zwischen gewöhnlicher Temperatur und 100°C liegen ; besonders vorteilhaft ist eine Temperatur von etwa 50 bis 70° C. The polymerization in the dilution medium can be carried out in the presence of a free radical forming catalyst in a closed vessel in an inert Atmosphere and under autogenous pressure or additional pressure or in an open vessel be carried out under reflux at normal pressure. The temperature can be between ordinary temperature and 100 ° C; a temperature is particularly advantageous from about 50 to 70 ° C.
Geeignete, freie Radikale bildende Katalvsatoren sind Peroxyverbindungen, wie Natrium-, Kalium-und Ammoniumpersulfate, Caprylylperoxyd, Benzoylperoxyd, Wasserstoffperoxyd, Pelargonylperoxyd, Cumolhydroperoxyd, tert.-Butyldiperphthalat, tert.-Butylperbenzoat, Natriumperacetat und Natriumpercarbonat, wie auch Azodiisobuttersäurenitril. Andere geeignete Katalysatoren sind Redox-und mit Schwermetall aktivierte Katalysatorsysteme. Suitable catalysts which form free radicals are peroxy compounds, such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, Pelargonyl peroxide, cumene hydroperoxide, tert-butyl diperphthalate, tert-butyl perbenzoate, Sodium peracetate and sodium percarbonate, as well as azodiisobutyronitrile. Other suitable catalysts are redox and heavy metal activated catalyst systems.
Beispiel In der folgenden Tabelle werden einige Beispiele für gemäß
dieser Erfindung hergestellte Polymerisate von Acryl-und Methacrylsäure und die
Viskosität einer 1, beige benzolischen Lösung derselben angegeben.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1103585XA | 1954-01-18 | 1954-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1103585B true DE1103585B (en) | 1961-03-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG22766A Pending DE1103585B (en) | 1954-01-18 | 1955-01-17 | Process for the production of acrylic and methacrylic acid polymers and copolymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1103585B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1178599B (en) * | 1961-03-28 | 1964-09-24 | Maroquinerie Nationale Sa | Process for the production of copolymers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1043830A (en) * | 1951-10-13 | 1953-11-12 | Nobel Francaise Soc | New synthetic resins |
-
1955
- 1955-01-17 DE DEG22766A patent/DE1103585B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1043830A (en) * | 1951-10-13 | 1953-11-12 | Nobel Francaise Soc | New synthetic resins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1178599B (en) * | 1961-03-28 | 1964-09-24 | Maroquinerie Nationale Sa | Process for the production of copolymers |
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