DE1210189B - Process for the production of mixed polymers of methacrylic acid methyl ester - Google Patents
Process for the production of mixed polymers of methacrylic acid methyl esterInfo
- Publication number
- DE1210189B DE1210189B DE1960R0029241 DER0029241A DE1210189B DE 1210189 B DE1210189 B DE 1210189B DE 1960R0029241 DE1960R0029241 DE 1960R0029241 DE R0029241 A DER0029241 A DE R0029241A DE 1210189 B DE1210189 B DE 1210189B
- Authority
- DE
- Germany
- Prior art keywords
- production
- methyl ester
- methacrylic acid
- acid methyl
- acid imide
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 229960002317 succinimide Drugs 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NEHSDFGBKFTKLJ-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-1-en-2-ylbenzene Chemical compound COC(=O)C(C)=C.CC(=C)C1=CC=CC=C1 NEHSDFGBKFTKLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- 238000009757 thermoplastic moulding Methods 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- 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
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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)
Description
Verfahren zur Herstellung von Mischpolymerisaten des Methacrylsäuremethylesters Thermoplastische Formmassen, d. h. Kunststoffe, die nach dem Preß-, Preßspritz-, Spritzguß-, Strangpreß- oder nach dem Walzverfahren verarbeitet werden, sollen eine hohe Wärmeformbeständigkeit, die z. B. durch die Vicat-Erweichungstemperatur bestimmt wird, bei möglichst guter Verarbeitbarkeit aufweisen. Die Verarbeitbarkeit hängt außer vom Fließverhalten auch von der Thermostabilität ab.Process for the production of copolymers of methyl methacrylate Thermoplastic molding compounds, d. H. Plastics that are produced after compression molding, compression molding, Injection molding, extrusion or by the rolling process are to be processed high heat resistance, the z. B. determined by the Vicat softening temperature will have, with the best possible processability. The workability depends apart from the flow behavior, it also depends on the thermal stability.
Darunter versteht man, daß das Material bei der Verarbeitungstemperatur noch nicht depolymerisiert.This means that the material is at the processing temperature not yet depolymerized.
Erwünscht ist ein möglichst großer Spielraum in der Verarbeitungstemperatur, um auch schwierige Teile herstellen, vornehmlich spritzen zu können.The greatest possible latitude in the processing temperature is desirable, in order to be able to manufacture even difficult parts, primarily to be able to inject.
Mischpolymerisate aus Methacrylsäuremethylester und a-Methylstyrol zeichnen sich durch einen hohen Erweichungspunkt aus, d. h., die daraus hergestellten Formkörper sind z. B. in kochendem Wasser formbeständig. Die Thermostabilität dieser Mischpolymerisate ist jedoch unbefriedigend; sie beginnen bei der für die Verarbeitung erforderlichen Temperatur zu depolymerisieren. Dieser Abbau kann beim Verspritzen zu Schlieren- und Blasenbildung im Formteil führen. Copolymers of methyl methacrylate and α-methylstyrene are characterized by a high softening point, i. i.e., those made from it Shaped bodies are z. B. dimensionally stable in boiling water. The thermostability of this Copolymers are unsatisfactory, however; they start with for processing required temperature to depolymerize. This breakdown can occur when splashing lead to streaking and blistering in the molded part.
Es ist auch bereits bekannt, Methacrylsäuremethylester zusammen mit a-Methylstyrol und einem weiteren Monomeren, wie Acrylnitril, Styrol oder Acrylsäureester, zu polymerisieren. It is also already known to use methyl methacrylate together with a-methylstyrene and another monomer, such as acrylonitrile, styrene or acrylic acid ester, to polymerize.
Es wurde nun gefunden, daß bei einem Verfahren zur Herstellung von Mischpolymerisaten durch Block-oder Perlpolymerisation von überwiegenden Mengen an Methacrylsäuremethylester und 5 bis 30 Gewichtsprozent a-Methylstyrol zusammen mit anderen polymerisierbaren Monomeren in Gegenwart von Beschleunigern, gegebenenfalls von Reglern, bei Temperaturen von 50 bis 130"C dann neben der Erhöhung der Erweichungstemperatur gleichzeitig eine Verbesserung der Thermostabilität erzielt wird, wenn man als anderes polymerisierbares Monomeres 2 bis 20 Gewichtsprozent N-Vinylbernsteinsäureimid oder N-Vinylphthalsäureimid einsetzt. It has now been found that in a process for the production of Copolymers by block or bead polymerization in predominant amounts of methyl methacrylate and 5 to 30 percent by weight of α-methylstyrene with other polymerizable monomers in the presence of accelerators, if appropriate of regulators, at temperatures from 50 to 130 "C then in addition to increasing the softening temperature at the same time an improvement in thermal stability is achieved if one as another polymerizable monomer 2 to 20 weight percent N-vinyl succinic acid imide or N-vinylphthalic acid imide is used.
Die Mischpolymerisate, gemäß dem Verfahren der Erfindung hergestellt, erlauben den Spritzguß auch von komplizierten Formteilen. Sie bringen also im Hinblick auf ihre technische Verwertbarkeit deutliche Vorteile. The copolymers produced according to the process of the invention allow the injection molding of complex molded parts. So you bring in view clear advantages in terms of their technical usability.
Die Herstellung der Mischpolymerisate erfolgt in an sich bekannter Weise durch Block- oder Perlpolymerisation in Gegenwart eines Beschleunigers bei 50 bis 130"C. Als Beschleuniger sind Verbindungen wie Azodiisobuttersäurenitril oder Peroxyde geeignet. Im besonderen Maße haben sich Kombinationen aus Azodiisobuttersäurenitril mit einem eine hohe Zerfallstemperatur besitzenden Peroxyd, wie tert.Butylhydroperoxyd oder tert.Butylperbenzoat, bewährt. The copolymers are produced in a manner known per se Way by block or bead polymerization in the presence of an accelerator 50 to 130 "C. Compounds such as azodiisobutyronitrile are used as accelerators or peroxides suitable. Combinations of azodiisobutyronitrile have proven to be particularly good with a peroxide that has a high decomposition temperature, such as tert-butyl hydroperoxide or tert-butyl perbenzoate, proven.
Außerdem haben sich Kombinationen aus einem niedrig- und einem hochzerfallenden Peroxyd, wie aus Dilauroylperoxyd zusammen mit tert.Butylhydroperoxyd, als zweckmäßig erwiesen. In addition, there are combinations of a low-decay and a high-decay Peroxide, such as from dilauroyl peroxide together with tert-butyl hydroperoxide, is useful proven.
Mit besonderem Vorteil kann man die Polymerisation mit Schwefelreglern, wie Mercaptanen, leiten. The polymerization with sulfur regulators, like mercaptans, conduct.
Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß durch die Mitverwendung von N-Vinylbernsteinsäureimid oder N-Vinylphthalsäureimid die Polymerisationsgeschwindigkeit der radikalisch initiierten Methylmethacrylat-a-Methylstyrol-Mischpolymerisation gesteigert wird. Another advantage of the method according to the invention is that that by using N-vinyl succinic acid imide or N-vinyl phthalic acid imide the polymerization rate of the radical initiated methyl methacrylate-α-methylstyrene copolymerization is increased.
Man erhält glasklare Polymerisate, die praktisch ungefärbt sind. Crystal-clear polymers which are practically uncolored are obtained.
Außer den bereits genannten guten Eigenschaften der neuen Mischpolymerisate, nämlich außer einem hohen Erweichungspunkt und einer guten Thermostabilität, verdient ihre Wasserunempfindlichkeit hervorgehoben zu werden. In addition to the already mentioned good properties of the new copolymers, namely, apart from a high softening point and good thermal stability, deserves their insensitivity to water to be emphasized.
In der nachstehenden Tabelle ist die Vicat-Erweichungstemperatur
von bekannten Polymerisaten mit der von erfindungsgemäß hergestellten Mischpolynerisaten
zum Vergleich angeführt. Die Anteile sind Gewichtsprozente.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1960R0029241 DE1210189B (en) | 1960-12-08 | 1960-12-08 | Process for the production of mixed polymers of methacrylic acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1960R0029241 DE1210189B (en) | 1960-12-08 | 1960-12-08 | Process for the production of mixed polymers of methacrylic acid methyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1210189B true DE1210189B (en) | 1966-02-03 |
Family
ID=602309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1960R0029241 Pending DE1210189B (en) | 1960-12-08 | 1960-12-08 | Process for the production of mixed polymers of methacrylic acid methyl ester |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1210189B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636458A (en) * | 1982-12-30 | 1987-01-13 | Rohm Gmbh | Storage disk made of para-methyl styrene |
| US4754008A (en) * | 1986-04-16 | 1988-06-28 | Rohm Gmbh | Heat resistant molding compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2862907A (en) * | 1957-04-01 | 1958-12-02 | Monsanto Chemicals | Suspension process for the polymerization of vinylidene aromatic hydrocar-bons having rubbery conjugated 1, 3-diene polymers dissolved therein |
| US2862906A (en) * | 1957-04-01 | 1958-12-02 | Monsanto Chemcial Company | Suspension process for the polymerization of vinylidene aromatic hydrocarbons |
| GB836837A (en) * | 1956-01-23 | 1960-06-09 | Baker Chem Co J T | Improvements to polymerization products |
-
1960
- 1960-12-08 DE DE1960R0029241 patent/DE1210189B/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB836837A (en) * | 1956-01-23 | 1960-06-09 | Baker Chem Co J T | Improvements to polymerization products |
| US2862907A (en) * | 1957-04-01 | 1958-12-02 | Monsanto Chemicals | Suspension process for the polymerization of vinylidene aromatic hydrocar-bons having rubbery conjugated 1, 3-diene polymers dissolved therein |
| US2862906A (en) * | 1957-04-01 | 1958-12-02 | Monsanto Chemcial Company | Suspension process for the polymerization of vinylidene aromatic hydrocarbons |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636458A (en) * | 1982-12-30 | 1987-01-13 | Rohm Gmbh | Storage disk made of para-methyl styrene |
| US4754008A (en) * | 1986-04-16 | 1988-06-28 | Rohm Gmbh | Heat resistant molding compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1107940B (en) | Process for the manufacture of a thermoplastic product which contains a substantial amount of graft copolymer | |
| DE1669625A1 (en) | Molding and casting compounds for the production of transparent thermoplastic moldings with improved impact strength | |
| EP0033365A1 (en) | Process for the preparation of impact-resistant moulding masses | |
| DE2048722A1 (en) | Thermoplastic molding compounds | |
| DE1569486B2 (en) | THERMOPLASTIC MOLDING COMPOUND | |
| EP0526813A1 (en) | Polymer alloys containing ethylene polymers for flexible foils | |
| DE1182811B (en) | Thermoplastic molding compounds based on styrene and acrylonitrile | |
| CH626642A5 (en) | ||
| DE1210189B (en) | Process for the production of mixed polymers of methacrylic acid methyl ester | |
| DE1089550B (en) | Process for the production of rigid, tough, weather-resistant, dimensionally stable, polymeric plastic products from methacrylic acid and acrylic acid esters | |
| DE4440219A1 (en) | Process for the preparation of copolymers from alkyl methacrylate, vinyl aromatics and maleic anhydride | |
| DE1231013B (en) | Process for the production of copolymers | |
| EP0321832A2 (en) | Mixtures of rubbery thermoplastic polymers | |
| ES400796A1 (en) | Vinyl chloride resin compositions | |
| DE2045742B2 (en) | TRANSPARENT, IMPACT TOUGH MOLDING | |
| DE1132725B (en) | Process for the production of copolymers with an extremely heterogeneous structure | |
| DE1720802B2 (en) | Thermoplastic-elastic molding compounds | |
| DE3730205A1 (en) | METHOD FOR PRODUCING Graft Polymers | |
| DE1694471C3 (en) | Thermoplastic masses | |
| DE1669630C3 (en) | Process for the preparation of graft polymers | |
| DE1109893B (en) | Process for the production of impact-resistant polystyrenes | |
| AT259225B (en) | Polymerization process | |
| DE1569102B2 (en) | Thermoplastic molding compound | |
| DE2914841A1 (en) | METHOD FOR MANUFACTURING VULCANIZABLE ACRYLIC ELASTOMERS | |
| DE1495691A1 (en) | Process for the production of impact-resistant polystyrene compositions |