DE1495520C3 - - Google Patents
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- Publication number
- DE1495520C3 DE1495520C3 DE19641495520 DE1495520A DE1495520C3 DE 1495520 C3 DE1495520 C3 DE 1495520C3 DE 19641495520 DE19641495520 DE 19641495520 DE 1495520 A DE1495520 A DE 1495520A DE 1495520 C3 DE1495520 C3 DE 1495520C3
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- DE
- Germany
- Prior art keywords
- minutes
- acid
- dimethyl
- compounds
- peroxide
- 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.)
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- 238000000034 method Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- NFQAQKVFBFWVKQ-UHFFFAOYSA-N 1,3-dimethyl-5-(2-methylpropyl)-1,3-diazinane-2,4,6-trione Chemical compound CC(C)CC1C(=O)N(C)C(=O)N(C)C1=O NFQAQKVFBFWVKQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- AMQCWPDDXYOEER-UHFFFAOYSA-N 3-cyano-2-butanone Chemical compound N#CC(C)C(C)=O AMQCWPDDXYOEER-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- QSQMLMUBVHLHFM-UHFFFAOYSA-N 2-methyl-3-oxo-3-phenylpropanenitrile Chemical compound N#CC(C)C(=O)C1=CC=CC=C1 QSQMLMUBVHLHFM-UHFFFAOYSA-N 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- OTSKHUNLOQPIGN-UHFFFAOYSA-N 1,3,5-trimethyl-1,3-diazinane-2,4,6-trione Chemical compound CC1C(=O)N(C)C(=O)N(C)C1=O OTSKHUNLOQPIGN-UHFFFAOYSA-N 0.000 description 10
- -1 hydrochlorides tertiary amines Chemical class 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- HNYOPLTXPVRDBG-UHFFFAOYSA-N Barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- ODYNBECIRXXOGG-UHFFFAOYSA-N N-butylbutan-1-amine;hydron;chloride Chemical compound [Cl-].CCCC[NH2+]CCCC ODYNBECIRXXOGG-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N Phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OAUFZDJROJSXGE-UHFFFAOYSA-N dibutyl(2-phenylethyl)azanium;chloride Chemical compound Cl.CCCCN(CCCC)CCC1=CC=CC=C1 OAUFZDJROJSXGE-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ILIMOFAFBPEQAT-UHFFFAOYSA-N 1,5,5-trimethyl-1,3-diazinane-2,4,6-trione Chemical compound CN1C(=O)NC(=O)C(C)(C)C1=O ILIMOFAFBPEQAT-UHFFFAOYSA-N 0.000 description 1
- DCGGMHIZEAHUJL-UHFFFAOYSA-N 1-methyl-1,3-diazinane-2,4,6-trione Chemical compound CN1C(=O)CC(=O)NC1=O DCGGMHIZEAHUJL-UHFFFAOYSA-N 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N Dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M Dioctyl sodium sulfosuccinate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- LEHSOUZQZPUDEC-UHFFFAOYSA-N N-butyl-N-(2-phenylethyl)butan-1-amine Chemical compound CCCCN(CCCC)CCC1=CC=CC=C1 LEHSOUZQZPUDEC-UHFFFAOYSA-N 0.000 description 1
- 229920001225 Polyester resin Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229940027983 antiseptics and disinfectants Quaternary ammonium compounds Drugs 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000399 orthopedic Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001356 surgical procedure Methods 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Description
Es ist bekannt, die Polymerisation bzw. die Copolymerisation von Vinylverbindungen, beispielsweise Estern der Acrylsäure oder der Methacrylsäure, und ungesättigten Polyestern in Gegenwart von Luft, Sauerstoff und/oder peroxidischen Verbindungen, gegebenenfalls unter Anwendung erhöhter Temperaturen, durchzuführen. Es ist ferner bekannt, für diese Polymerisationen neben den Katalysatoren Beschleuniger einzusetzen. Bekannt sind für diese Zwecke beispielsweise tertiäre Amine (DT-PS 9 75 072), Verbindungen, die ein labiles Halogenatom enthalten, wie Salze der Halogenwasserstoffsäuren, Hydrochloride tertiärer Amine, Chloride von Oniumverbindungen, beispielsweise quaternären Ammoniumverbindungen, Esterchloride u. dgl. Außerdem hat man für dieselben Zwecke schon organische Schwefelverbindungen, wie Λ-Aminosulfone, a-Oxysulfone, Merkaptane, Sulfinsäuren und deren Salze usw., angewendet (DT-PS 1014 327, 10 03 448, 1110 868, 9 55 633, 9 13 477, 9 16 733).It is known, the polymerization or the copolymerization of vinyl compounds, for example Esters of acrylic acid or methacrylic acid, and unsaturated polyesters in the presence of air, Oxygen and / or peroxidic compounds, if necessary using elevated temperatures, perform. It is also known to use accelerators in addition to the catalysts for these polymerizations to use. Are known for this purpose, for example, tertiary amines (DT-PS 9 75 072), compounds, which contain a labile halogen atom, such as salts of hydrohalic acids, hydrochlorides tertiary amines, chlorides of onium compounds, for example quaternary ammonium compounds, Ester chlorides and the like. In addition, organic sulfur compounds have already been used for the same purposes, such as Λ-aminosulfones, a-oxysulfones, mercaptans, sulfinic acids and their salts etc., applied (DT-PS 1014 327, 10 03 448, 1110 868, 9 55 633, 9 13 477, 9 16 733).
Es ist außerdem bekannt, zum Härten ungesättigter Polyesterharzmassen als Katalysatoren Phenylacetaldehyd und/oder dessen am Benzolkern substituierte Derivate zu verwenden. Für die gleichen Zwecke hat man auch schon a-monosubstituierte Phenylacetaldehyde für sich allein, gegebenenfalls in Kombination mit anderen Katalysatoren, sowie a-Iminobuttersäureester, eingesetzt (DT-PS1144479,1151115; DT-AS 10 87 349).It is also known to use phenylacetaldehyde as catalysts for curing unsaturated polyester resin compositions and / or to use its derivatives substituted on the benzene nucleus. Has for the same purposes you can also use α-monosubstituted phenylacetaldehydes on their own, possibly in combination with other catalysts, as well as a-iminobutyric acid ester, used (DT-PS1144479,1151115; DT-AS 10 87 349).
Mit Hilfe dieser Polymerisationsstartsysteme lassen sich technisch interessante Ergebnisse erzielen. Nachteilig fällt jedoch in manchen Fällen eine nachträgliche Verfärbung ins Gewicht.With the help of these polymerization start systems, technically interesting results can be achieved. Disadvantageous In some cases, however, subsequent discoloration is significant.
Es wurde nun gefunden, daß man Ester der Acryl- und Methacrylsäure, Acrylnitril, Vinylacetat, Styrol, einzeln oder im Gemisch, vorzugsweise in Gegenwart ihrer Polymerisate, und ungesättigte Polyester, vorzugsweise in Gegenwart von anpolymerisierbaren Monomeren, in Gegenwart von organischen Peroxiden,It has now been found that esters of acrylic and methacrylic acid, acrylonitrile, vinyl acetate, styrene, individually or in a mixture, preferably in the presence of their polymers, and unsaturated polyesters, preferably in the presence of polymerizable monomers, in the presence of organic peroxides,
ίο gegebenenfalls in Gegenwart von Beschleunigern, in Substanz polymerisieren kann, wenn man in Gegenwart entweder von a-Benzoylpropionitril oder a-Acetylpropionitril oder in Gegenwart von 1,3,5-Trimethyl-, l,3-Dimethyl-5-phenyl- oder l,3-Dimethyl-5-isobutylbarbitursäure polymerisiert.ίο possibly in the presence of accelerators, in Substance can polymerize when in the presence of either a-benzoylpropionitrile or a-acetylpropionitrile or in the presence of 1,3,5-trimethyl-, 1,3-dimethyl-5-phenyl- or 1,3-dimethyl-5-isobutylbarbituric acid polymerized.
Vorteilhaft fällt bei diesem Verfahren die Beständigkeit der erhaltenen Produkte gegen Einwirkung von
Wasser und nachträgliche Verfärbung ins Gewicht.
Es ist zwar aus der GB-PS 6 84 489 bekannt, bei der Polymerisation von Styrol u. a. Barbitursäure oder
eine substituierte Barbitursäure zu verwenden, um den gefährlichen Umgang mit teuren peroxidischen
Katalysatoren zu vermeiden. Diese Polymerisation muß jedoch bei Temperaturen von 1000C durchgeführt
werden und führt nicht zu wasserbeständigen Produkten, die sich nachträglich nicht mehr verfärben.In this process, the resistance of the products obtained to the action of water and subsequent discoloration is advantageous.
It is known from GB-PS 6 84 489 to use, inter alia, barbituric acid or a substituted barbituric acid in the polymerization of styrene in order to avoid the dangerous handling of expensive peroxidic catalysts. However, this polymerization has to be carried out at temperatures of 100 ° C. and does not lead to water-resistant products which subsequently no longer discolor.
Auch die nach dem Verfahren der US-PS 2610965Also according to the method of US Pat. No. 2,610,965
erhaltenen Produkte weisen diese Eigenschaften nicht auf, weil die Polymerisation außer in Gegenwart bestimmter Peroxide, nämlich α,α-Dialkylarylmethylhydroperoxide, auch in Gegenwart von Ammoniak, Aminen oder Hydrazin durchgeführt werden muß.obtained products do not have these properties, because the polymerization except in the presence of certain Peroxides, namely α, α-dialkylarylmethyl hydroperoxides, must also be carried out in the presence of ammonia, amines or hydrazine.
Nichtverfärbende Polymerisate können auch nicht nach dem Verfahren gemäß US-PS 29 00 360 und 23 80 618 erhalten werden, weil die nach diesem Verfahren mitzuverwendenden schwefelhaltigen Verbindungen ebenfalls zu stark gelbverfärbten Produkten führen.Non-discoloring polymers can also not by the process according to US Pat. No. 2,900,360 and 23 80 618 are obtained because the sulfur-containing compounds to be used according to this process also lead to strongly yellow discolored products.
Unter den im Anspruch 1 genannten Verbindungen muß insbesondere die in 5-Stellung alkylsubstituierte Barbitursäure wegen ihrer guten Löslichkeit in Wasser und/oder organischen Lösungsmitteln hervorgehoben werden.Among the compounds mentioned in claim 1, in particular that which is alkyl-substituted in the 5-position must be Barbituric acid highlighted because of its good solubility in water and / or organic solvents will.
In einzelnen Fällen kann die Löslichkeit der genannten Verbindung durch Zugabe von beispielsweise Dioxan oder Dimethylformamid verbessert werden.In individual cases, the solubility of the compound mentioned can be increased by adding, for example Dioxane or dimethylformamide can be improved.
Durch die gute Löslichkeit ergibt sich eine größere Variationsbreite bei deren Einsatz.The good solubility results in a greater range of variation in their use.
Die erfindungsgemäß einzusetzenden Katalysatoren können an sich in beliebigen Mengen verwendet werden. Die obere Grenze wird in erster Linie durch die Wirtschaftlichkeit festgelegt. Beispielsweise kann man ohne weiteres Mengen von 10% anwenden. Im allgemeinen arbeitet man jedoch in Mengen von etwa 0,05 bis etwa 6 Gewichtsprozent, vorzugsweise von etwa 0,5 bis etwa 3 Gewichtsprozent, bezogen auf das Monomere.The catalysts to be used according to the invention can per se be used in any desired amounts. The upper limit is primarily determined by economic efficiency. For example, you can without further ado use amounts of 10%. In general, however, one works in amounts of about 0.05 to about 6 percent by weight, preferably from about 0.5 to about 3 percent by weight, based on the Monomers.
Zur Verkürzung der Polymerisationszeiten empfiehlt es sich, neben den erfindungsgemäß einzusetzenden Stoffen zusätzlich in an sich bekannter Weise weitere Beschleuniger mitzuverwenden. Insbesondere kommen hierfür Verbindungen, die ionogen gebundenes Halogen enthalten bzw. leicht Halogenionen, vorzugsweise Chlorionen, bilden, in Frage. Außerdem kann man in vorteilhafter Weise für die gleichen Zwecke die sogenannten Pseudohalogenide, zu denen die Rhodanide, Cyanide und Azide gehören, einsetzen. Ferner ist insbesondere auch die Mitverwendung von Schwermetall-To shorten the polymerization times, it is advisable to use in addition to those to be used according to the invention Substances additionally to use further accelerators in a manner known per se. In particular, come for this purpose compounds which contain ionogenically bound halogen or slightly halogen ions, preferably Chlorine ions, form, in question. In addition, you can use the so-called in an advantageous manner for the same purposes Pseudohalides, to which the rhodanides, cyanides and azides belong, use. Furthermore, in particular also the use of heavy metal
3 43 4
verbindungen, vorzugsweise von Kupferverbindungen, 1,3,5-Trimethylbarbitursäure + ρ,ρ'-Dichlor-compounds, preferably of copper compounds, 1,3,5-trimethylbarbituric acid + ρ, ρ'-dichloro
vorteilhaft. Von besonderem Vorteil ist die Kombi- dibenzoylperoxid 27,0%advantageous. Of particular advantage is the combi- dibenzoyl peroxide 27.0%
nation der Halogenide mit den Schwermetallen. a-Benzoyipropionitril ohne Zusatz 13,2%nation of the halides with the heavy metals. a-Benzoyipropionitrile without additives 13.2%
Weitere an sich bekannte Beschleuniger, die im Ä_Benzoylpropionitril + 30vol.-%ige H2O2-Other per se known accelerators, which are obtainable in Ä _ B + enzoylpropionitril 30Vol .-% H 2 O 2 -
Polymensationsgemisch anwesend sein können, sind 5 Lösung /0022Polymerization mixture can be present are 5 solution / 0022
organische Schwefelverbindungen, wie a-Amino- und _. ' .'".". 'organic sulfur compounds such as a-amino and _. '.' ".". '
«-Oxysulfone und Merkaptane, sowie vorzugsweise «-Benzolypropiomtnl + tert.-Butylhydro-«-Oxysulfones and mercaptans, and preferably« -Benzolypropiomtnl + tert-butylhydro-
Alkohole, insbesondere die einwertigen primären und peroxid 14,6 /0 Alcohols, especially the monohydric primary and peroxide 14.6 / 0
sekundären.secondary.
Alle genannten weiteren Beschleuniger können in an 10 B e i s ρ i e 1 2
sich bekannten Mengen angewendet werden.All other accelerators mentioned can be used in an 10 B eis ρ ie 1 2
known amounts are used.
Unter den organischen Peroxiden kommen insbeson- Es wird eine Lösung hergestellt aus 52 ecm Meth-Among the organic peroxides, in particular, a solution is made from 52 ecm meth-
dere die Diacyl- und die Hydroperoxide in Frage. Be- acrylsäuremethylester (entstabilisiert), 1,5 mg Hydro-the diacyl and hydroperoxides in question. Be acrylic acid methyl ester (destabilized), 1.5 mg hydro-
vorzugt werden aber die Acylalkylperoxide, zum Bei- chinon, 4 mg Kupferacetylacetonat und 1 ecm Me-However, preference is given to the acylalkyl peroxides, for the bei- quinone, 4 mg of copper acetylacetonate and 1 ecm of me-
spiel das tert.-Butylperbenzoat, eingesetzt. 15 thanol. Eine kleine Menge Dibutylaminhydrochloridplay the tert-butyl perbenzoate, used. 15 ethanol. A small amount of dibutylamine hydrochloride
Monomere bzw. Comonomere, die im Rahmen wird zugegeben und die damit gesättigte LösungMonomers or comonomers, which is added in the frame and the solution saturated with it
dieser Erfindung polymerisiert werden können, sind filtriert.This invention can be polymerized are filtered.
insbesondere Methacrylsäuremethylester, ferner Acryl- 1,8 ecm dieser Lösung werden mit 3 g polymeremin particular methacrylic acid methyl ester, furthermore acrylic 1.8 ecm of this solution are mixed with 3 g of polymeric
nitril, Styrol, Vinylacetat. Bei der Durchführung des Methacrylsäuremethylester (Perlmaterial), 1 % (30 g)nitrile, styrene, vinyl acetate. When performing the methyl methacrylate (pearl material), 1% (30 g)
Verfahrens kann man auch in an sich bekannter Weise 20 l,3-Dimethyl-5-phenyl-barbitursäureso wiel % p,p'-Di-Process can also be used in a manner known per se 20 l, 3-dimethyl-5-phenyl-barbituric acid as% p, p'-di-
von dem System Pulver-Flüssigkeit ausgehen. chlorbenzoylperoxid verrührt. Bei einer Ausgangs-proceed from the powder-liquid system. stirred chlorobenzoyl peroxide. At an exit
Vorteilhaft geht man von solchen Ansätzen aus, die temperatur von 25 0C wird nach 5 Minuten eine
ein Polymerisat der genannten Monomeren ganz oder maximale Temperatur von 960C erreicht,
teilweise in einem oder mehreren der genannten Monomeren gelöst enthalten. Die polymeren Stoffe können 25 B e i s ρ i e 1 3
gegebenenfalls auch ungesättigte polymerisierbareIt is advantageous to start from such approaches, the temperature of 25 0 C is reached after 5 minutes a polymer of the monomers mentioned completely or a maximum temperature of 96 0 C,
partly dissolved in one or more of the monomers mentioned. The polymeric substances can 25 B bis ρ ie 1 3
optionally also unsaturated polymerizable
Bindungen enthalten, wie es beispielsweise bei den Beispiel 2 wird wiederholt, jedoch wird ein Geungesättigten Polyestern der Fall ist. misch aus Methacrylsäuremethylester und Acrylsäure-Contain bonds, as is repeated, for example, in Example 2, but one is unsaturated Polyesters is the case. mixture of methacrylic acid methyl ester and acrylic acid
Vorzugsweise geht man jedoch von solchen siru- nitril verwendet. Nach 6 Minuten wird eine maximale
pösen Ansätzen aus, die das Polymerisat in Form 3° Temperatur von 1070C erreicht,
eines in an sich bekannter Weise durch partielle Polymerisation gewonnenen Vorpolymerisats enthalten. Beispiel 4However, preference is given to using such sirunitrile. After 6 minutes, a maximum of pöse approaches, which the polymer reaches in the form of 3 ° temperature of 107 0 C,
contain a prepolymer obtained in a manner known per se by partial polymerization. Example 4
Die Polymerisation kann in Gegenwart von an sichThe polymerization can take place in the presence of per se
bekannten Füll-, Farbstoffen, Pigmenten, Verstär- Zu 10 g Polyestergießharz werden 0,5% 1,3,5-Tri-known fillers, dyes, pigments, reinforcements. To 10 g polyester casting resin, 0.5% 1,3,5-tri
kungsmitteln sowie Stabilisatoren, wie Hydrochinon, 35 methylbarbitursäure, 0,5% Phenyläthyldibutylamin-agents and stabilizers such as hydroquinone, 35 methylbarbituric acid, 0.5% phenylethyldibutylamine
durchgeführt werden. hydrochlorid, 10 ppm Cu++ (als Naphthenat) und 2%be performed. hydrochloride, 10 ppm Cu + + (as naphthenate) and 2%
Das erfindungsgemäße Verfahren kann beispiels- einer 50%igen Lauroylperoxidpaste (in Dioctyl-The inventive method can, for example, a 50% lauroyl peroxide paste (in dioctyl
weise bei der Herstellung bzw. Anwendung von ebenen adipat) zugegeben. Der Ansatz ist nach 3 Minutenwisely in the production or use of planar adipate) added. The approach is after 3 minutes
oder gewellten, gegebenenfalls verstärkten Platten geliert und nach 5 Minuten unter starker Erwärmungor corrugated, optionally reinforced sheets and gelled after 5 minutes under intense heating
sowie bei Füll-, Gieß-, Ausfüll- und Anstrich- oder 40 völlig erhärtet.as well as with filling, pouring, filling and painting or completely hardened.
Klebemassen verwendet werden. Beispiel 5Adhesives are used. Example 5
Das Verfahren kann mit besonderem Erfolg auchThe procedure can also be particularly successful
auf dem Gebiet der Human- und Veterinärmedizin Zu 15 ml unstabilisiertem monomerem Methylsowie
auf dem zahnärztlichen und zahntechnischen methacrylat werden 1,0% 1,3,5-Trimethylbarbitur-Gebiet
durchgeführt werden, beispielsweise bei der 45 säure, 0,2% Phenyläthyldibutylaminhydrochlorid und
Anwendung von Abdruckmassen, Modellmassen und 10 ppm Cu++ (als Naphthenat) sowie 1,0% reines
Füllmassen, bei der Herstellung von Prothesen, Ein- Lauroylperoxid zugegeben und durch kurzes Umbettungen
und Fixierungen sowie bei der Herstellung schütteln gelöst. Durch Messung der Brechungszahl
von Geräten und Apparaten in der Orthopädie, η2S wird der Polymerisationsverlauf verfolgt.
Chirurgie und Kieferorthopädie. 50in the field of human and veterinary medicine to 15 ml of unstabilized monomeric methyl as well as on the dental and dental technical methacrylate 1.0% 1,3,5-trimethylbarbitur area are carried out, for example in the 45 acid, 0.2% phenylethyldibutylamine hydrochloride and application of impression materials, model materials and 10 ppm Cu + + (as naphthenate) as well as 1.0% pure filling materials, when manufacturing prostheses, one-lauroyl peroxide is added and dissolved by brief re-embedding and fixation and shaking during manufacture. The course of the polymerization is followed by measuring the refractive index of devices and apparatus in orthopedics, η 2 S.
Surgery and orthodontics. 50
n . -11 Zeit nach Zugabe aller Brechungszahl n . -11 time after adding all refractive indices
Beispiel 1 Substanzen „20 Example 1 Substances “20
2 ecm reiner Methacrylsäuremethylester (entstabili- 2 ecm of pure methacrylic acid methyl ester (destabilized
siert) werden mit 20mg 1,3,5-Trimethylbarbitursäure 55 ,T , .....siert) with 20mg 1,3,5-trimethylbarbituric acid 55, T , .....
bzw. «-Benzoyl-propionitril, 12 γ Kupferacetylaceto- Nach 20 Minuten 1,4357or «-Benzoyl-propionitrile, 12 γ copper acetylaceto- After 20 minutes 1.4357
nat in 0,1 ecm Methanol, 2 mg Dibutylaminhydrochlo- Nach 27 Minuten 1,4528nat in 0.1 ecm methanol, 2 mg dibutylamine hydrochloride- After 27 minutes 1.4528
rid, ebenfalls in 0,2 ecm Methanol, und 1 % eines (hochviskoser Sirup)rid, also in 0.2 ecm of methanol, and 1% of a (highly viscous syrup)
Peroxids versetzt. Es wird bei 25°C polymerisiert. Das Nach 32 Minuten fest Peroxide added. It is polymerized at 25 ° C. That stuck after 32 minutes
jeweils verwendete Peroxid sowie die nach 30 Minuten 60each peroxide used and that after 30 minutes 60
erhaltene Polymerisatmenge sind in der nachfolgendenThe amount of polymer obtained is as follows
Tabelle zusammengefaßt: VergleichsversuchTable summarized: comparative experiment
1,3,5-Trimethylbarbitursäure ohne Zusatz ... 27,0% Es wird wie im Beispiel 5 beschrieben verfahren.1,3,5-Trimethylbarbituric acid without addition ... 27.0% The procedure is as described in Example 5.
1,3,5-Trimethylbarbitursäure + 30vol-%ige ^ 65 Zum Vergleich wird ohne Trimethylbarbitursäure1,3,5-trimethylbarbituric acid + 30% by volume ^ 6 5 For comparison, without trimethylbarbituric acid
HjjOj-Lösung 32,3 % gearbeitet. Der Ansatz ist nach Zugabe der einzelnenHjjOj solution 32.3% worked. The approach is after adding each
1,3,5-Trimethylbarbitursäure + tert.-Butyl- Substanzen gelbgrünlich und zeigt nach 3 Tagen noch1,3,5-trimethylbarbituric acid + tert-butyl substances yellow-greenish and still shows after 3 days
hydroperoxid 35,3% keine weitere Veränderung der Viskosität.hydroperoxide 35.3% no further change in viscosity.
Es wird wie im Beispiel 5 beschrieben verfahren. Die verschiedenen Substanzen werden jedoch in folgenden Mengen zugesetzt:The procedure described in Example 5 is followed. However, the various substances are discussed in the following Amounts added:
0,5 % 1,3,5-Trimethylbarbitursäure,0.5% 1,3,5-trimethylbarbituric acid,
0,1 % Phenyläthyldibutylaminhydrochlorid0.1% phenylethyldibutylamine hydrochloride
2,0 ppm Cu++2.0 ppm Cu + +
0,5 % Lauroylperoxid0.5% lauroyl peroxide
farbloses Polymerisatcolorless polymer
Beispiel 7 einer Konzentration von 5,3 · 10~2 Mol/l vorhanden.Example 7 e i ner concentration of 5.3 x 10 -2 mol / l available.
2 ecm Vinylacetat werden mit 12,3 γ Kupfer(II)- Es wird bei 250C polymerisiert und der Umsatz durch acetylacetonat und 1,98 mg Dibutylaminhydrochlorid Titration mit Brom bestimmt. Die verwendeten (jeweils gelöst in 0,1 ecm Methanol) versetzt. Der Initiatoren und die Ergebnisse sind in der nachInitiator und das Peroxid (Lauroylperoxid) sind in 30 folgenden Tabelle wiedergegeben:2 ecm of vinyl acetate are with 12.3 γ copper (II) - It is polymerized at 25 0 C and the conversion is determined by acetylacetonate and 1.98 mg of dibutylamine hydrochloride titration with bromine. The used (each dissolved in 0.1 ecm of methanol) were added. The initiators and the results are shown in the following table:
Initiatorinitiator
Umsatz in % nachSales in% after
Minuten 20 Minuten 30 Minuten 40 Minuten 60 MinutenMinutes 20 minutes 30 minutes 40 minutes 60 minutes
1,3,5-Trimethylbarbitursäure l,3-Dimethyl-5-isobutylbarbitursäure Λ-Acetylpropionitril1,3,5-trimethylbarbituric acid 1,3-Dimethyl-5-isobutylbarbituric acid Λ-acetylpropionitrile
24,224.2
3232
18,818.8
21,121.1
Es wird wie im Beispiel 7 beschrieben verfahren, jedoch wird als Monomeres Styrol verwendet und bei 350C polymerisiert. Die Umsatzbestimmung erfolgt durch Fällen mit Methanol und Auswiegen. Die Initiatoren und die Ergebnisse sind in der nachfolgenden Tabelle wiedergegeben:The procedure is as described in Example 7, but is used as a monomer of styrene and polymerized at 35 0 C. The conversion is determined by precipitation with methanol and weighing. The initiators and the results are shown in the table below:
Initiatorinitiator
Umsatz in % nachSales in% after
Minuten 60 MinutenMinutes 60 minutes
90 Minuten90 minutes
l,3-Dimethyl-5-isobutylbarbitursäure 1,3,5-Trimethylbarbitursäure Λ-Acetylpropionitril1,3-dimethyl-5-isobutylbarbituric acid 1,3,5-trimethylbarbituric acid Λ-acetylpropionitrile
Initiatorinitiator
Umsatz in % nachSales in% after
Minuten 30 Minuten 40 Minuten 60 Minuten 90 MinutenMinutes 30 minutes 40 minutes 60 minutes 90 minutes
l,3-Dimethyl-5-isobutylbarbitursäure + Lauroylperoxid1,3-Dimethyl-5-isobutylbarbituric acid + lauroyl peroxide
l,3-Dimethyl-5-isobutylbarbitursäure + ρ,ρ'-Dichlordibenzoylperoxid 1,3,5-Trimethylbarbitursäure + Lauroylperoxid1,3-Dimethyl-5-isobutylbarbituric acid + ρ, ρ'-dichlorodibenzoyl peroxide 1,3,5-trimethylbarbituric acid + lauroyl peroxide
1,3,5-Trimethylbarbitursäure + ρ,ρ'-Dichlordibenzoylperoxid
a-Acetylpropionitril + Lauroylperoxid a-Acetylpropionitril + ρ,ρ'-Dichlordibenzoylperoxid
1,3,5-trimethylbarbituric acid + ρ, ρ'-dichlorodibenzoyl peroxide
α-acetylpropionitrile + lauroyl peroxide α-acetylpropionitrile + ρ, ρ'-dichlorodibenzoyl peroxide
4,64.6
4,96.4
4.9
7,19.1
7.1
Es wird wie im Beispiel 8 beschrieben verfahren, jedoch wird bei 25° C polymerisiert. Die Initiatoren und die Ergebnisse sind in der nachstehenden Tabelle aufgeführt:The procedure is as described in Example 8, but polymerisation is carried out at 25 ° C. The initiators and the Results are shown in the table below:
Initiator Umsatz in % nachInitiator conversion in% after
30 Minuten 60 Minuten 90 Minuten 180 Minuten30 minutes 60 minutes 90 minutes 180 minutes
1,3,5-Trimethylbarbitursäure + ρ,ρ'-Dichlordibenzoyl- 3,1 5,4 6,1 9,91,3,5-trimethylbarbituric acid + ρ, ρ'-dichlorodibenzoyl- 3.1 5.4 6.1 9.9
peroxidperoxide
1,3,5-Trimethylbarbitursäure + Lauroylperoxid 2,9 5,2 7,7 12,01,3,5-trimethylbarbituric acid + lauroyl peroxide 2.9 5.2 7.7 12.0
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED0044322 | 1964-05-02 | ||
| DED0044322 | 1964-05-02 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1495520A1 DE1495520A1 (en) | 1969-04-10 |
| DE1495520B2 DE1495520B2 (en) | 1970-06-25 |
| DE1495520C3 true DE1495520C3 (en) | 1976-09-16 |
Family
ID=7048237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19641495520 Granted DE1495520B2 (en) | 1964-05-02 | 1964-05-02 | Method of polymerizing |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3347954A (en) |
| BE (1) | BE663329A (en) |
| CH (1) | CH479633A (en) |
| DE (1) | DE1495520B2 (en) |
| DK (1) | DK129417B (en) |
| GB (1) | GB1110673A (en) |
| NL (1) | NL143947B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE538514A (en) * | 1954-05-28 | |||
| DE1060590B (en) * | 1957-08-27 | 1959-07-02 | Basf Ag | Process for the production of molded bodies and coatings |
| US3031301A (en) * | 1959-03-30 | 1962-04-24 | Gen Electric | Photosensitive resin compositions |
-
1964
- 1964-05-02 DE DE19641495520 patent/DE1495520B2/en active Granted
-
1965
- 1965-04-01 CH CH453265A patent/CH479633A/en not_active IP Right Cessation
- 1965-04-09 DK DK182965AA patent/DK129417B/en unknown
- 1965-04-27 US US451350A patent/US3347954A/en not_active Expired - Lifetime
- 1965-04-29 GB GB18137/65A patent/GB1110673A/en not_active Expired
- 1965-04-29 NL NL656505490A patent/NL143947B/en unknown
- 1965-04-30 BE BE663329A patent/BE663329A/xx unknown
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