CA1170799A - Process for the continuous preparation of rubber-modified polymers of vinylaromatics - Google Patents
Process for the continuous preparation of rubber-modified polymers of vinylaromaticsInfo
- Publication number
- CA1170799A CA1170799A CA000380031A CA380031A CA1170799A CA 1170799 A CA1170799 A CA 1170799A CA 000380031 A CA000380031 A CA 000380031A CA 380031 A CA380031 A CA 380031A CA 1170799 A CA1170799 A CA 1170799A
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- CA
- Canada
- Prior art keywords
- weight
- monomer
- rubber
- conversion
- amount
- 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.)
- Expired
Links
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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
Abstract
O.Z. 0050/034517 Abstract of the Disclosure: A process, carried out without a diluent or in solution, in more than 2 reaction zones, for the continuous preparation of rubber-modified polymers of vinylaromatics, wherein a monomeric aromatic vinyl compound and an elastomeric polymer, in an amount of from 3 to 16% by weight based on the monomer, are polymerized, in the absence of a free radical initiator, but in the presence of a mercaptan as a chain transfer agent, at from 80 to 180°C in a first reaction zone, with stirring, up to a maximum monomer conversion, Umax, given by the equation Umax = K - 1 where K is the amount of rubber in % by weight based on monomer, and, in a second reaction zone, polymerization is continued, with stirring, to a conversion of up to about 50% by weight, after which a chain transfer agent is introduced in an amount of from 0.01 to 0.2% by weight, based on vinyl-aromatic monomer, and polymerization is continued, if appropriate in more than one reaction zone, up to a monomer conversion of less than 85% by weight.
The polymer is treated in a devolatilization zone to remove vinyl-aromatic monomer and solvent, if any, and these constituents are recycled to the process.
The process claimed makes it possible to prepare products which exhibit good gloss coupled with good mechanical properties, and which can be employed for con-ventional applications.
The polymer is treated in a devolatilization zone to remove vinyl-aromatic monomer and solvent, if any, and these constituents are recycled to the process.
The process claimed makes it possible to prepare products which exhibit good gloss coupled with good mechanical properties, and which can be employed for con-ventional applications.
Description
117~9~
- 1 - O.Z. 0050/034517 Process for the continuous preparation of rubber-modified polvmers of vin~la~omatics m e present invention relates to a continuous process for the preparation of rubber-modi~ied polymers of vinylaromatics. m e process is carried out in the absence of a free radical initiator and in the presence of a mercaptan as a chain transfer agent.
The relevant prior art includes (1) U.S a Patent 3,90~,202, (2) U.S. Patent 3,243,481, (3) U.S, Patent 3,914,339 and (4) U.S. Patent 3,428,712.
The continuous polymerization of high-impact poly-styrene in two, three or more reaction zones has beenknown for a long time [Q~. (1) or t2)~. It is also known that chain transfer agents, eg nitroso-containing compounds or mercaptans, may be used to adjust the molecular weight [c~. (1), (2) and (4)]. (3) further-more proposes that the chain regulator be added a~ter a certain conversion, which is from 3.5 to 15% by weight, has been reached.
According to the teachi~g of (3), the polymeriza-tion is initially carried out as a mass polymerization, in the absence of an initiator. After the chain trans- !
fer agent has been added, polymerization is continued to a conversion of 20-40% by weight, and thereafter the reaction is completed in a third stage, in the presence of lauroyl peroxide. The process described gives products having hlgh gloss and containing small rubber particles. However, the disadv~tage of the known .
117~ 799
- 1 - O.Z. 0050/034517 Process for the continuous preparation of rubber-modified polvmers of vin~la~omatics m e present invention relates to a continuous process for the preparation of rubber-modi~ied polymers of vinylaromatics. m e process is carried out in the absence of a free radical initiator and in the presence of a mercaptan as a chain transfer agent.
The relevant prior art includes (1) U.S a Patent 3,90~,202, (2) U.S. Patent 3,243,481, (3) U.S, Patent 3,914,339 and (4) U.S. Patent 3,428,712.
The continuous polymerization of high-impact poly-styrene in two, three or more reaction zones has beenknown for a long time [Q~. (1) or t2)~. It is also known that chain transfer agents, eg nitroso-containing compounds or mercaptans, may be used to adjust the molecular weight [c~. (1), (2) and (4)]. (3) further-more proposes that the chain regulator be added a~ter a certain conversion, which is from 3.5 to 15% by weight, has been reached.
According to the teachi~g of (3), the polymeriza-tion is initially carried out as a mass polymerization, in the absence of an initiator. After the chain trans- !
fer agent has been added, polymerization is continued to a conversion of 20-40% by weight, and thereafter the reaction is completed in a third stage, in the presence of lauroyl peroxide. The process described gives products having hlgh gloss and containing small rubber particles. However, the disadv~tage of the known .
117~ 799
- 2 - O.Z. 0050/03~517 process is that a substàntial proportion of low molecular weight polymers are formed; the latter lower the softening point of the finished product and tend to exude on pro-cessing Furthermore~ these low molecular weight con-stituents lower the impact strength if little or no in~tiator is used [cf. (3)]. On the other hand~ how-ever, the initiator concentrations employed in (3) lead to uncontrollable reactions if a continuous mass polymeri-zation or solution polymerization is carried out.
~t is an object of the present invention to pro-vide a continuous polymerization process which ob~iates the use of initiators and nevertheless gives products having`good gloss and containing small rubber particles, without this being at the expense o~ the mechanical pro-perties.
We have found that this object is achieved, surprisingly, if the chain transfer agent is introduced after the second process stage and if furthermore the reaction is not taken to complete conversion but is~
instead, stopped before then. This surprising effect was in no way foreseeable, especially since (4) recom-mends that the reaction be taken to the highest possible conversion.
Accordingly, the present invention relates to a process for the continuous preparation of a rubber- -modified polymer of a vinylaromatic, wherein a mixture which contains one or more monomeric aromatic vinyl compounds and from 3 to 16% by weight, based on mono-mers, of one or more elastomeric polymers consisting 1~'7~ 9
~t is an object of the present invention to pro-vide a continuous polymerization process which ob~iates the use of initiators and nevertheless gives products having`good gloss and containing small rubber particles, without this being at the expense o~ the mechanical pro-perties.
We have found that this object is achieved, surprisingly, if the chain transfer agent is introduced after the second process stage and if furthermore the reaction is not taken to complete conversion but is~
instead, stopped before then. This surprising effect was in no way foreseeable, especially since (4) recom-mends that the reaction be taken to the highest possible conversion.
Accordingly, the present invention relates to a process for the continuous preparation of a rubber- -modified polymer of a vinylaromatic, wherein a mixture which contains one or more monomeric aromatic vinyl compounds and from 3 to 16% by weight, based on mono-mers, of one or more elastomeric polymers consisting 1~'7~ 9
- 3 - O.Z. 0050~03~517 principally o~ polymerized 1J3-diene units, with or with-out a solvent, is polymerized, in the absence of a free radical initiator but in the presence of a mercaptan as a chain transfer agent, at from 80 to 180CI
a) in a ~irst process stage, with stirring, up to a maximum conversion Umax~ based on mo:nomer or monomers, given by the equation U = K - l .
where K is the amount of rubber în % by weight, based on monomer or monomers, b) is then poly~erized further, in a second pro-cess stage, with stirring, to a conversion of up to about 50% by welght, and c) is then polymerized further, in one or more additional process stages, after which the polymer is treated in a devolatilization zone to remove vinyl-aromatic monomers and solvents, if any, and these con-stituents are recycled to the process, wherein the chain transfer agent is introduced after the second process stage b), in an amount of from 0.01 to 0.2% by weight, based on vinyl-aromatic monomer, and the polymerization in process stage or stages c) is taken to a monomer con- !
version of less than 85~ by weight.
m e continuous preparation of rubber-modified polymers of vinylaromatics has been ade~uately described, :: especially in (2) (cf. the kettle-tower cascade principle), ~ so that reference may be made to this publication for ; details concerning the method of carrying out the con-tinuous process.
-117~7~9 - ~ _ o.z~ oOSo/034517 Suitable aromatic vinyl compounds ~or the process according to the invention are styrene and its derivatives, eg. ~-meth~lstyrene, o-,m- and p-methylstyrene, 2,4-dimethylstyrene and tert.-butylstyrene. Styrene is preferred.
The ~lastomeric polymer, consistingprincipallyof polymeri~ed 1,3-diene units, does not have to conform to any special requirements. Both natural and synthetic polybutadienes may be used, as well as polyisoprene rubbers, styrene-butadiene block copolymers of the SB
type, and three-block copolymers of the BSB or SBS type.
Diene rubbers which contain about 10% by weight of L,2-vinyl units, or high-cis gradesg with more than 96% by weight of the cis-structure, are particularly preferred~
The process according to the in~ention can be carried out in the absence of a diluent or in solution.
In the case of mass polymerization, the rubber is dis-solved in the vinyl-aromatic monomer to be polymerized, and the polymerization is then started. Suitable sol-vents are toluene, xylene, ethylbenzene, methyl ethylketone and tetrahydrofuran. The amount of solvents used is from 2 to 15% by weight, based on monomer or monomers. Ethylbenzene, used in the stated amounts, is a particularly preferred solvent.
Suitable chain transfer agents for the process according to the invention are the conventionally used - mercaptans of 1 to 14 carbon atoms; tert.-dodecylmer-captan has proved particularly suitable. The amount of mercaptan is as a rule from 0.01 to 0.2% by weight, _ 5 _ o~z. 0050~034517 based on vinyl-aromatic monomer. Within this range, the exact amount depends on the desired melt flow of the polymers to be prepared. For technical reasons, such as accuracy of dosing, and ease of mixing-in, it is advan-tageous if the chain transfer agent is not employed in the pure ~orm but as a solution in a solvent, such as toluene, ethylbenzene? xylene or meth~l ethyl ketone, or together with a lubricant, such as paraffin oil or butyl stearate, or as a mixture with a small amount o~ the monomer. I~ the regulator is introduced in the first sta~e of the process, the surface roughness of articles produced from the polymers is excessi~e, and the gloss inadequate. Accordingly, the regulator must be added a~ter the first process stage, and in par-ticular should not be added before the conversion has reached 20% by weight. Where the process is carried out in more than two stages, it is preferred to introduce the regulator in the third process stage. In two-stage processes, such as are described, for example, in (1), the regulator is of course introduced into the second stage; however/ this is only useful if the con-version in~he first stage is greater than 20% by weight.
The method o~ carrying out the first and all subsequent process stages is known to a skilled worker, who also knows that stirring in -the second process stage is critical. Equally, the temperatures to be used in the various process stages are familiar to a skilled worker. TakLng all the process stages, the polymerl-~ .
, 13L7a~99 -- 6 - o.Z. OOSo/034517 zation temperatures lie within a range of from 80 to 180C. In the drying stage or devolatilization stage, even higher temperatures are used.
It is essential that the final conversion in the second stage, or in a further stage, depending on whether the process employs two or more stages, is restricted to less than 85% by weight, based on monomer. This con-version proves to be critical in the process according to the invention; whilst higher conversions would be lo desirable per se, the mechanical properties of the poly-mers obtained become substantially less good. The conversion can be easily calculated from the solids content, which in turn can be determined by methods ~amiliar to a skilled worker. For example, a sample can be taken, in which the unconverted monomer is determined titri--metrically, or from which the monomer can be evaporated off after stabilization with a polymerization inhibitor, and the residue determined gravimetrically.
The product properties referred to in the Examples and Comparative Experiments were measured as follows:
1. Yield stre~s in accordance with DIN 53,455 2. Tensile strength according to DIN 53,455 3. Melt index according to DIN 53,735
a) in a ~irst process stage, with stirring, up to a maximum conversion Umax~ based on mo:nomer or monomers, given by the equation U = K - l .
where K is the amount of rubber în % by weight, based on monomer or monomers, b) is then poly~erized further, in a second pro-cess stage, with stirring, to a conversion of up to about 50% by welght, and c) is then polymerized further, in one or more additional process stages, after which the polymer is treated in a devolatilization zone to remove vinyl-aromatic monomers and solvents, if any, and these con-stituents are recycled to the process, wherein the chain transfer agent is introduced after the second process stage b), in an amount of from 0.01 to 0.2% by weight, based on vinyl-aromatic monomer, and the polymerization in process stage or stages c) is taken to a monomer con- !
version of less than 85~ by weight.
m e continuous preparation of rubber-modified polymers of vinylaromatics has been ade~uately described, :: especially in (2) (cf. the kettle-tower cascade principle), ~ so that reference may be made to this publication for ; details concerning the method of carrying out the con-tinuous process.
-117~7~9 - ~ _ o.z~ oOSo/034517 Suitable aromatic vinyl compounds ~or the process according to the invention are styrene and its derivatives, eg. ~-meth~lstyrene, o-,m- and p-methylstyrene, 2,4-dimethylstyrene and tert.-butylstyrene. Styrene is preferred.
The ~lastomeric polymer, consistingprincipallyof polymeri~ed 1,3-diene units, does not have to conform to any special requirements. Both natural and synthetic polybutadienes may be used, as well as polyisoprene rubbers, styrene-butadiene block copolymers of the SB
type, and three-block copolymers of the BSB or SBS type.
Diene rubbers which contain about 10% by weight of L,2-vinyl units, or high-cis gradesg with more than 96% by weight of the cis-structure, are particularly preferred~
The process according to the in~ention can be carried out in the absence of a diluent or in solution.
In the case of mass polymerization, the rubber is dis-solved in the vinyl-aromatic monomer to be polymerized, and the polymerization is then started. Suitable sol-vents are toluene, xylene, ethylbenzene, methyl ethylketone and tetrahydrofuran. The amount of solvents used is from 2 to 15% by weight, based on monomer or monomers. Ethylbenzene, used in the stated amounts, is a particularly preferred solvent.
Suitable chain transfer agents for the process according to the invention are the conventionally used - mercaptans of 1 to 14 carbon atoms; tert.-dodecylmer-captan has proved particularly suitable. The amount of mercaptan is as a rule from 0.01 to 0.2% by weight, _ 5 _ o~z. 0050~034517 based on vinyl-aromatic monomer. Within this range, the exact amount depends on the desired melt flow of the polymers to be prepared. For technical reasons, such as accuracy of dosing, and ease of mixing-in, it is advan-tageous if the chain transfer agent is not employed in the pure ~orm but as a solution in a solvent, such as toluene, ethylbenzene? xylene or meth~l ethyl ketone, or together with a lubricant, such as paraffin oil or butyl stearate, or as a mixture with a small amount o~ the monomer. I~ the regulator is introduced in the first sta~e of the process, the surface roughness of articles produced from the polymers is excessi~e, and the gloss inadequate. Accordingly, the regulator must be added a~ter the first process stage, and in par-ticular should not be added before the conversion has reached 20% by weight. Where the process is carried out in more than two stages, it is preferred to introduce the regulator in the third process stage. In two-stage processes, such as are described, for example, in (1), the regulator is of course introduced into the second stage; however/ this is only useful if the con-version in~he first stage is greater than 20% by weight.
The method o~ carrying out the first and all subsequent process stages is known to a skilled worker, who also knows that stirring in -the second process stage is critical. Equally, the temperatures to be used in the various process stages are familiar to a skilled worker. TakLng all the process stages, the polymerl-~ .
, 13L7a~99 -- 6 - o.Z. OOSo/034517 zation temperatures lie within a range of from 80 to 180C. In the drying stage or devolatilization stage, even higher temperatures are used.
It is essential that the final conversion in the second stage, or in a further stage, depending on whether the process employs two or more stages, is restricted to less than 85% by weight, based on monomer. This con-version proves to be critical in the process according to the invention; whilst higher conversions would be lo desirable per se, the mechanical properties of the poly-mers obtained become substantially less good. The conversion can be easily calculated from the solids content, which in turn can be determined by methods ~amiliar to a skilled worker. For example, a sample can be taken, in which the unconverted monomer is determined titri--metrically, or from which the monomer can be evaporated off after stabilization with a polymerization inhibitor, and the residue determined gravimetrically.
The product properties referred to in the Examples and Comparative Experiments were measured as follows:
1. Yield stre~s in accordance with DIN 53,455 2. Tensile strength according to DIN 53,455 3. Melt index according to DIN 53,735
4. Mean particle size by counting on electron micro-graphs.
5. Gloss by means of a Dr. Lange Multiflex galvano-meter. For this purpose, the products obtained were injection-molded at 260C, and the relative reflectance .. ~
_ 7 _ 0.2~ 0050~034517 from the surface of these moldings was measured as a percentage of t~e incident light. The standard used was Pilter paper, having a reflectance of 0%.
m e Examples and Comparative Experiments which follow illustrate the invention. All parts and per-centages are by weight, unless stated otherwise.
EXAMPI,E 1 A mixture of 7~2 parts of a polybutadiene con-taining 98% o~ cis-units, 85.7 parts o styrene, 6 parts of ethylbenzene and 0.1 part o~ octadecyl 3-(~',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate was polymerized thermally in a 2-kettle 2-tower cascade. The through-put was 4 llters/hour. The stirring speeds and tem-peratures employed in the individual reactors, and the cumulative conversions obtained, are shown in Table 1.
In the third reactor, 0.02% by weight, based on styrene, o~ tert -dodecylmercaptan, dissolved in paraffin oil, was introduced continuously into the polymer stream.
~fter polymerization, the mixture obtained was freed from solvent and residual monomer in a devolatilization zone at 220-240C. The properties of the product obtained, together with those of the products from Comparative Experiments 1 and 2, are shown in Table 2.
Example 1 was repeated, except that the chain transfer agent was introduced continuously into the first process stage. In Table 2, the properties of the pro-duct obtained are compared with those of the product of - 8 - O.Z. 0050/034517 Example 1. It is seen that the yield stress, tensile strength and gloss are greatly reduced i~ the chain transfer agent is introduced into the first process stage a).
7.78;parts of polybutadiene, 85.12 parts of styrene and 701 parts of solvent were polymerized con-tinuously, by the method described in Example 1, with thedifference that in the fourth process stage the polymeri-~ation was only stopped when the conversion was 92%.
The conversions at the various stages were:
Reactor Conversion (%) Kettle 1 ~3 Kettle 2 22.2 Tower 1 53.4 Tower 2 92.0 The properties of the product obtained are shown in Table 2. It is seen, on comparison with the pro-ducts according to the present invention, that increasing the conversion reduces the toughness.
.
, ., ~::L7~799 _ g _ o.zO oOSo/034517 Position Stirring speed Te erature Con~ersion Crpm] m~oc~(cumulative) 1st stirred reactor 100 104 3.8 2nd stirred reactor 160 132 20.3 1st tower 15 101 55.3 2nd tower 3 127 84~3 Devolatili-æation - 250 Example Comparative Comparative 1 E~perimen-t Experiment Yield stress CN/mm2] 27.3 22.6 26.8 Tensile strength [N/mm2] 22.5 19.1 21.7 Notched impact strength [kJ/m2] 10.5 10.4 8.5 Melt index (5/200) Cg/lo'~ 3.0 2~6 3.9 Mean particle size [~m~1.2 3.5 1.4 G1RSS (ref1eC~enCe) [~151,4 22.6 47.8 ' ~ ; .
_ 7 _ 0.2~ 0050~034517 from the surface of these moldings was measured as a percentage of t~e incident light. The standard used was Pilter paper, having a reflectance of 0%.
m e Examples and Comparative Experiments which follow illustrate the invention. All parts and per-centages are by weight, unless stated otherwise.
EXAMPI,E 1 A mixture of 7~2 parts of a polybutadiene con-taining 98% o~ cis-units, 85.7 parts o styrene, 6 parts of ethylbenzene and 0.1 part o~ octadecyl 3-(~',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionate was polymerized thermally in a 2-kettle 2-tower cascade. The through-put was 4 llters/hour. The stirring speeds and tem-peratures employed in the individual reactors, and the cumulative conversions obtained, are shown in Table 1.
In the third reactor, 0.02% by weight, based on styrene, o~ tert -dodecylmercaptan, dissolved in paraffin oil, was introduced continuously into the polymer stream.
~fter polymerization, the mixture obtained was freed from solvent and residual monomer in a devolatilization zone at 220-240C. The properties of the product obtained, together with those of the products from Comparative Experiments 1 and 2, are shown in Table 2.
Example 1 was repeated, except that the chain transfer agent was introduced continuously into the first process stage. In Table 2, the properties of the pro-duct obtained are compared with those of the product of - 8 - O.Z. 0050/034517 Example 1. It is seen that the yield stress, tensile strength and gloss are greatly reduced i~ the chain transfer agent is introduced into the first process stage a).
7.78;parts of polybutadiene, 85.12 parts of styrene and 701 parts of solvent were polymerized con-tinuously, by the method described in Example 1, with thedifference that in the fourth process stage the polymeri-~ation was only stopped when the conversion was 92%.
The conversions at the various stages were:
Reactor Conversion (%) Kettle 1 ~3 Kettle 2 22.2 Tower 1 53.4 Tower 2 92.0 The properties of the product obtained are shown in Table 2. It is seen, on comparison with the pro-ducts according to the present invention, that increasing the conversion reduces the toughness.
.
, ., ~::L7~799 _ g _ o.zO oOSo/034517 Position Stirring speed Te erature Con~ersion Crpm] m~oc~(cumulative) 1st stirred reactor 100 104 3.8 2nd stirred reactor 160 132 20.3 1st tower 15 101 55.3 2nd tower 3 127 84~3 Devolatili-æation - 250 Example Comparative Comparative 1 E~perimen-t Experiment Yield stress CN/mm2] 27.3 22.6 26.8 Tensile strength [N/mm2] 22.5 19.1 21.7 Notched impact strength [kJ/m2] 10.5 10.4 8.5 Melt index (5/200) Cg/lo'~ 3.0 2~6 3.9 Mean particle size [~m~1.2 3.5 1.4 G1RSS (ref1eC~enCe) [~151,4 22.6 47.8 ' ~ ; .
Claims
O.Z. 0050/034517 we claim:-A process for the continuous preparation of a rubber modified polymer of a vinylaromatic, wherein a mixture which contains one or more monomeric aromatic vinyl compounds and from 3 to 16% by weight; based on monomers) of one or more elastomeric polymers consisting principally of polymerized 1,3-diene units, with or with-out a solvent, is polymerized, in the absence of a free radical initiator but in the presence of a mercaptan as a chain transfer agent, at from 80 to 180°C, a) in a first process stage, with stirring, up to a maximum conversion Umax, based on monomer or monomers, given by the equation Umax = K - 1 where K is the amount of rubber in % by weight, based on monomer or monomers, b) is then polymerized further, in a second pro-cess stage, with stirring, to a conversion of up to about 50% by weight, and c) is then polymerized further, in one or more additional process stages, after which the polymer is treated in a devolatilization zone to remove vinyl-aromatic monomers and solvents, if any, and these con-stituents are recycled to the process, wherein the chain transfer agent is introduced after the second process stage b), in an amount of from 0.01 to 0.2% by weight, based on vinyl-aromatic monomer, and the polymerization in process stage or stages c) is taken to a monomer con-version of less than 85% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3023721.9 | 1980-06-25 | ||
| DE19803023721 DE3023721A1 (en) | 1980-06-25 | 1980-06-25 | METHOD FOR THE CONTINUOUS PRODUCTION OF RUBBER-MODIFIED POLYMERISATS OF VINYL FLAVORS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1170799A true CA1170799A (en) | 1984-07-10 |
Family
ID=6105403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380031A Expired CA1170799A (en) | 1980-06-25 | 1981-06-17 | Process for the continuous preparation of rubber-modified polymers of vinylaromatics |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4427826A (en) |
| EP (1) | EP0042985B1 (en) |
| CA (1) | CA1170799A (en) |
| DE (2) | DE3023721A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4777210A (en) * | 1986-07-25 | 1988-10-11 | Cosden Technology, Inc. | Continuous production of high impact polystyrene |
| USH1278H (en) | 1988-08-31 | 1994-01-04 | Shell Oil Company | Elastomeric, ceramic fiber reinforced polyketone polymer blends |
| KR100409074B1 (en) * | 2000-12-01 | 2003-12-11 | 주식회사 엘지화학 | Method for preparing rubber-modified styrene transparent resin having superior fluidity |
| US6506847B1 (en) | 2001-08-08 | 2003-01-14 | Basell Poliolefine Italia S.P.A. | Controlling the molecular weight of graft copolymers using polymerizable chain transfer agents |
| CA2645436A1 (en) * | 2006-03-28 | 2007-10-04 | Council Of Scientific & Industrial Research | Water-soluble macromonomers containing terminal unsaturation and a process for the preparation thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3243481A (en) | 1962-01-08 | 1966-03-29 | Dow Chemical Co | Process for making graft copolymers of vinyl aromatic compounds and stereospecific rubbers |
| FR1395954A (en) * | 1963-04-16 | 1965-04-16 | Rexall Drug Chemical | Manufacturing process of rubber modified polystyrene resins |
| US3428712A (en) | 1963-08-22 | 1969-02-18 | Rexall Drug Chemical | Process for obtaining polybutadiene-modified styrene resins |
| DE1645196A1 (en) * | 1965-03-12 | 1970-05-21 | Rexall Drug Chemical | Block solvent polymerization process for ABS polymers |
| US3945976A (en) * | 1968-09-30 | 1976-03-23 | Standard Oil Company | Process for producing impact resistant polymer |
| US3914339A (en) * | 1970-06-24 | 1975-10-21 | Sumitomo Chemical Co | Process for producing rubber-modified plastics |
| US3781383A (en) * | 1972-01-24 | 1973-12-25 | Foster Grant Co Inc | Impact vinyl aromatic polymers and their preparation |
| DE2320371A1 (en) | 1973-04-21 | 1974-11-07 | Celamerck Gmbh & Co Kg | THIOPHOSPHONIC ACID ESTER |
| US3903202A (en) * | 1973-09-19 | 1975-09-02 | Monsanto Co | Continuous mass polymerization process for polyblends |
| US4098847A (en) | 1974-03-11 | 1978-07-04 | Cosden Technology, Inc. | Process for making high impact polymers from diene polymer and vinyl aromatics |
| DE2613352B2 (en) | 1976-03-29 | 1980-08-07 | Basf Ag, 6700 Ludwigshafen | Process for the production of impact-resistant modified styrene polymers |
-
1980
- 1980-06-25 DE DE19803023721 patent/DE3023721A1/en not_active Withdrawn
-
1981
- 1981-06-02 DE DE8181104208T patent/DE3166145D1/en not_active Expired
- 1981-06-02 EP EP81104208A patent/EP0042985B1/en not_active Expired
- 1981-06-15 US US06/273,689 patent/US4427826A/en not_active Expired - Lifetime
- 1981-06-17 CA CA000380031A patent/CA1170799A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3023721A1 (en) | 1982-01-21 |
| DE3166145D1 (en) | 1984-10-25 |
| EP0042985A2 (en) | 1982-01-06 |
| EP0042985B1 (en) | 1984-09-19 |
| EP0042985A3 (en) | 1982-02-24 |
| US4427826A (en) | 1984-01-24 |
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