DE1301074B - Process for the preparation of polymerization products - Google Patents
Process for the preparation of polymerization productsInfo
- Publication number
- DE1301074B DE1301074B DE1964R0038168 DER0038168A DE1301074B DE 1301074 B DE1301074 B DE 1301074B DE 1964R0038168 DE1964R0038168 DE 1964R0038168 DE R0038168 A DER0038168 A DE R0038168A DE 1301074 B DE1301074 B DE 1301074B
- Authority
- DE
- Germany
- Prior art keywords
- polymerization
- chloride
- tertiary
- dimethyl
- sulfoxide
- 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
- 238000006116 polymerization reaction Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 2
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000012933 diacyl peroxide Substances 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 150000002432 hydroperoxides Chemical class 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-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
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerization Catalysts (AREA)
Description
Zur Polymerisation ungesättigter organischer Verbindungen bei vergleichsweise niederen Temperaturen verwendet man bekanntlich Redoxsysteme. Ein solches Redoxsystem besteht aus einer reduzierend und einer oxydierend wirkenden Verbindung. Bei den bekannten Polymerisationsverfahren werden als reduzierend wirkende Komponente tertiäre Amine, Sulfinsäure oder Mercaptane verwendet, während die oxydierend wirkende Komponente aus einem Peroxid besteht. For the polymerization of unsaturated organic compounds at comparatively Redox systems are known to be used at lower temperatures. Such a redox system consists of a reducing and an oxidizing compound. Both known polymerization processes are tertiary as a reducing component Amines, sulfinic acid or mercaptans are used as the oxidizing component consists of a peroxide.
Die Verwendung der obengenannten, an sich sehr wirksamen Redoxkomponenten ist mit Nachteilen verbunden. Tertiäre Amine haben die Neigung, dem Endprodukt eine unerwünschte Verfärbung zu geben, und die Anwendung von Sulfinsäuren ist infolge ihrer Unbeständigkeit unbequem. In Gegenwart von Mercaptanen wird nur dann eine rasche Polymerisation erzielt, wenn dem zu polymerisierenden Gemisch geringe Mengen einer Kupfer-Verbindung zugesetzt werden. Verfärbungen des Polymerisats durch Kupfer lassen sich dabei nicht immer vermeiden. Außerdem haben die bekannten Verfahren den Nachteil, daß sie unterhalb 15"C wenig oder gar nicht wirksam sind. The use of the above-mentioned redox components, which are per se very effective is associated with disadvantages. Tertiary amines have a tendency to give the end product an to give undesirable discoloration, and the use of sulfinic acids is a consequence inconvenient to their impermanence. In the presence of mercaptans, only one rapid polymerization achieved when the mixture to be polymerized is small a copper compound can be added. Discoloration of the polymer due to copper cannot always be avoided. In addition, the known methods the disadvantage that they are little or not at all effective below 15 "C.
Es wurde nun ein Verfahren zur Herstellung von Polymerisationsprodukten durch Polymerisation von Methacryl-, Acrylsäureestern, Styrolen oder Vinylestern in Masse ohne äußere Anwendung von Wärme in Gegenwart von Peroxiden, ausgenommen Dialkyl-und Diacylperoxide, und Beschleunigern gefunden, bei dem die obenerwähnten Nachteile nicht auftreten und zusätzlich die Reaktion erheblich beschleunigt wird, wenn als Polymerisationsbeschleuniger Säurechloride von ein- oder mehrbasischen gesättigten oder ungesättigten Fettsäuren bzw. von aromatischen Carbonsäuren zusammen mit Dialkylsulfoxid oder aliphatischen oder aromatischen Thioäthern verwendet werden. There has now been a method of making polymerization products by polymerizing methacrylic, acrylic acid esters, styrenes or vinyl esters in bulk without external application of heat in the presence of peroxides, except Dialkyl and diacyl peroxides, and accelerators found in the above mentioned Disadvantages do not occur and the reaction is also significantly accelerated, when used as a polymerization accelerator acid chlorides of monobasic or polybasic saturated or unsaturated fatty acids or aromatic carboxylic acids together with dialkyl sulfoxide or aliphatic or aromatic thioethers.
Die Verwendung eines Säurechlorids als Komponente eines Initiatorsystems ist zwar aus der französischen Patentschrift 1 069 088 bekannt. Nach diesem bekannten Verfahren wird jedoch das Initiatorsystem aus dem Säurechlorid und einem Arylsulfonalkylamin gebildet, und es konnte daraus nicht die Lehre gezogen werden, daß Hydroperoxyde mit Säurechloriden wirksame Systeme bilden. Während die Anwendbarkeit des Verfahrens der französischen Patentschrift auf einen Temperaturbereich von 15 bis 50"C beschränkt ist, kann mit dem erfindungsgemäßen Initiatorsystem noch bei Temperaturen um 0°C polymerisiert werden. The use of an acid chloride as a component of an initiator system is known from French patent specification 1,069,088. According to this well-known However, the process is the initiator system from the acid chloride and an arylsulfonalkylamine formed, and the lesson could not be drawn from it that hydroperoxides Form effective systems with acid chlorides. While the Applicability of the procedure the French patent is limited to a temperature range of 15 to 50 "C. is, can still at temperatures around 0 ° C with the initiator system according to the invention are polymerized.
Als Säurechlorid gemäß dem Verfahren der Erfindung sind gesättigte und ungesättigte Fettsäuren sowie aromatische Carbonsäuren geeignet, in denen die Hydroxylgruppe durch Chlor ersetzt ist. Neben den Säurechloriden von Monocarbonsäuren können mit gleich gutem Erfolg Säurechloride von mehrwertigen Carbonsäuren verwendet werden. As acid chloride according to the method of the invention are saturated and unsaturated fatty acids and aromatic carboxylic acids in which the Hydroxyl group is replaced by chlorine. In addition to the acid chlorides of monocarboxylic acids Acid chlorides of polybasic carboxylic acids can be used with equal success will.
Als Peroxide sind nach dem erfindungsgemäßen Verfahren besonders Hydroperoxide, wie tertiär-Butylhydroperoxid, Cumolhydroperoxid und Pinanhydroperoxid, geeignet. Außer mit Hydroperoxyden werden hohe Polymerisationsgeschwindigkeiten auch in Gegenwart von Mono-tertiär-Butylpermaleinat erzielt, insbesondere auch dann, wenn dieses in Mischung mit Hydroperoxiden vorliegt. Brauchbar, aber weniger wirksam als Hydroperoxide sind tertiär-Butylperoctoat, tertiär-Butylperacetat und tertiär-Butylperbenzoat. Dialkylperoxide und Diacylperoxide sind dagegen ungeeignet. Die als Aktivator dienenden Dialkylsulfoxide sowie aliphatischen und aromatischen Thioäther brauchen nur in geringen Mengen anwesend zu sein. Andere schwefelhaltige organische Verbindungen, wie Mercaptane, sind weitaus weniger wirksam als die genannten Thioäther oder Sulfoxide. Particularly useful peroxides in the process according to the invention are Hydroperoxides, such as tertiary butyl hydroperoxide, cumene hydroperoxide and pinane hydroperoxide, suitable. In addition to using hydroperoxides, polymerization rates are high also achieved in the presence of mono-tertiary-butylpermaleate, especially then, if this is present in a mixture with hydroperoxides. Useful but less effective as hydroperoxides are tertiary butyl peroctoate, tertiary butyl peracetate and tertiary butyl perbenzoate. Dialkyl peroxides and diacyl peroxides, on the other hand, are unsuitable. The ones that serve as an activator Dialkyl sulfoxides and aliphatic and aromatic thioethers only need in to be present in small quantities. Other sulfur-containing organic compounds, such as mercaptans, are far less effective than the thioethers or sulfoxides mentioned.
Als Monomere, die nach dem erfindungsgemäßen Verfahren in Substanz bei Temperaturen bis 0°C polymerisiert werden können, sind Acryl- und Methacrylsäureester, ferner Styrol und Vinylester geeignet. As monomers which, according to the process according to the invention, in substance can be polymerized at temperatures down to 0 ° C, are acrylic and methacrylic acid esters, styrene and vinyl ester are also suitable.
Das neue Initiatorsystem ist zur Herstellung von Dentalpräparaten, z. B. für die Herstellung von Prothesen, Dentalfüllungen und für Prothesenreparaturen geeignet. Weiterhin ist das erfindungsgemäße Vorhgehen zum Erhärten von Gießharzen auf Polyester- und Methacrylatbasis verwendbar. The new initiator system is for the production of dental preparations, z. B. for the production of prostheses, dental fillings and for prosthesis repairs suitable. Furthermore, the procedure according to the invention is for the hardening of casting resins Can be used on a polyester and methacrylate basis.
Die in der nachfolgenden Tabelle aufgeführten Beispiele 1 bis 9 beziehen sich auf 100 g einer 40010eigen Lösung von Polymethylmethacrylat in monomerem Methacrylsäuremethylester und auf eine Ausgangstemperatur von 21 C. Examples 1 to 9 listed in the table below relate to 100 g of a 40010eigen solution of polymethyl methacrylate in monomeric methyl methacrylate and to an initial temperature of 21 C.
Tabelle
Beispiel 11 In ein handelsübliches Gießharz aus 65 Gewichtsprozent Monostyrol und 35 Gewichtsprozent Polyester wurden bei 200 C unter Rühren folgende Komponenten des Initiatorsystems eingetragen: 1,00 0/o tertiär-Butylhydroperoxid, 0,95 % Mono-tertiär-Butylpermaleinat, 0,80 0/o Acetylchlorid, 0,050/0 Dimethylsulfoxid. Example 11 In a commercially available casting resin of 65 percent by weight Monostyrene and 35 percent by weight polyester were as follows at 200 ° C. with stirring Components of the initiator system entered: 1.00 0 / o tertiary butyl hydroperoxide, 0.95% mono-tertiary-butylpermaleate, 0.80% acetyl chloride, 0.050 / 0 dimethyl sulfoxide.
Die Polymerisation war nach 5 Minuten beendet, und das erreichte Temperaturmaximum betrug 140°C. The polymerization was complete in 5 minutes, and this accomplished The maximum temperature was 140 ° C.
Beispiel 12 Gemäß Beispiel 11 wurden 50g Vinylacetat bei 200 C polymerisiert. Die Polymerisation war nach 12 Minuten beendet, und die Temperatur stieg während der Polymerisation auf 126°C an. Das Polymerisat war glasklar und farblos. Example 12 As in Example 11, 50 g of vinyl acetate were polymerized at 200.degree. The polymerization was over after 12 minutes and the temperature rose during the polymerization to 126 ° C. The polymer was crystal clear and colorless.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1964R0038168 DE1301074B (en) | 1964-06-20 | 1964-06-20 | Process for the preparation of polymerization products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1964R0038168 DE1301074B (en) | 1964-06-20 | 1964-06-20 | Process for the preparation of polymerization products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1301074B true DE1301074B (en) | 1969-08-14 |
Family
ID=7405423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1964R0038168 Pending DE1301074B (en) | 1964-06-20 | 1964-06-20 | Process for the preparation of polymerization products |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1301074B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1069088A (en) * | 1954-03-01 | 1954-07-05 | Heraeus Gmbh W C | Process for increasing the activity of catalysts used in the preparation of polymerization products |
| DE1016935B (en) * | 1955-02-22 | 1957-10-03 | Degussa | Process for the polymerization of organic compounds |
| DE1049581B (en) * | 1954-07-30 | 1959-01-29 | Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, Frankfurt/M | Process for the polymerization of organic compounds |
| DE1128663B (en) * | 1961-03-21 | 1962-04-26 | Roehm & Haas Gmbh | Process for polymerizing monomeric unsaturated compounds |
-
1964
- 1964-06-20 DE DE1964R0038168 patent/DE1301074B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1069088A (en) * | 1954-03-01 | 1954-07-05 | Heraeus Gmbh W C | Process for increasing the activity of catalysts used in the preparation of polymerization products |
| DE1049581B (en) * | 1954-07-30 | 1959-01-29 | Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, Frankfurt/M | Process for the polymerization of organic compounds |
| DE1016935B (en) * | 1955-02-22 | 1957-10-03 | Degussa | Process for the polymerization of organic compounds |
| DE1128663B (en) * | 1961-03-21 | 1962-04-26 | Roehm & Haas Gmbh | Process for polymerizing monomeric unsaturated compounds |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E77 | Valid patent as to the heymanns-index 1977 |