CA1073596A - Monovinyl aromatic monomer-acrylonitrile copolymer and preparation thereof - Google Patents
Monovinyl aromatic monomer-acrylonitrile copolymer and preparation thereofInfo
- Publication number
- CA1073596A CA1073596A CA252,056A CA252056A CA1073596A CA 1073596 A CA1073596 A CA 1073596A CA 252056 A CA252056 A CA 252056A CA 1073596 A CA1073596 A CA 1073596A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- acrylonitrile
- weight
- copolymer
- aromatic monomer
- 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
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
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)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
ABSTRACT
Improved monovinyl aromatic monomer-acrylonitrile copolymers are prepared by mass polymerizing at temperatures above 80°C in the presence of certain free radical initi-ators, the resultant polymers are prepared at high rates of conversion, have relatively high heat distortion tem-peratures, have a low oligomer content and generate rela-tively little additional acrylonitrile under fabrication conditions. These copolymers are especially desirable for fabricating food containers.
17,703B-F
Improved monovinyl aromatic monomer-acrylonitrile copolymers are prepared by mass polymerizing at temperatures above 80°C in the presence of certain free radical initi-ators, the resultant polymers are prepared at high rates of conversion, have relatively high heat distortion tem-peratures, have a low oligomer content and generate rela-tively little additional acrylonitrile under fabrication conditions. These copolymers are especially desirable for fabricating food containers.
17,703B-F
Description
10'^~ 5'~
This invention provides an improved acrylonitrile resin which is easily fabricated, has improved thermal stability and a low extractable acrylonitrile content. ~-It further provides an improved process for the preparation of --monovinyl aromatic monomer-acrylonitrile copolymer resins which are thermally stable at injection molding temperatures, and which permits high conversion rates, and provides a resin having high heat distortion temperatures and a low acrylonitrile content, both before and after fabrication.
These benefits and other advantages in accordance with the present invention are achieved in a monovinyl aromatic mcnomer-acrylonitrile copolymer comprising from 9S to 25 parts by weight of a monovinyl aromatic monomer, from 5 to 75 parts by weight of acrylonitrile, the copolymer having a weight average of from 50,000 to 300,000 molecular weight units as determined by gel permeation chromatography employing a polystyrene standard, the copolymer containing not more than 7.5 x 10 5 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 3 parts by weight per part of copolymer of oligomers of styrene and acrylonitrile and characterized in that the polymer is prepared by mass polymerization at a temperature in excess of 80C.
Also within the scope of the present invention is a method fbr the preparation of a monovinyl aromatic monomer-acrylonitrile copolymer containing not more than 7.5 x 10 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 parts by weight, per part of co-polymer, of oligomers of styrene and acrylonitrile by providing a poly-merizable stream comprising from 5 to 75 parts by weight of L~
~ .:
~0'73~j9~
acrylonitrile and from 95 to 25 parts by weight of a monovinyl aromatic monomer, characterized in that the the stream contains from 5 X lO 5 to l X lO 2 parts by weight per part by weight of the polymerizable stream of a free radical initiating catalyst having a half-life of about one hour at a temperature in the range of 80C
to 180C, and maintaining the stream at a polymerization temperature sufficient to cause at least from 20 to 200 percent conversion of the monomer to polymer per hour.
Also within the scope of the present invention is an injection molded monovinyl aromatic monomer-acrylo-nitrile copolymer article, the article having as a princi-pal component thereof a mass-polymerized copolymer of from 5 to 75 parts by weight of acrylonitrile and from 95 to 25 parts by weight of alkenyl aromatic resinous monomer copolymerized therewith, and characterized by containing not more than 75 parts of residual acryloni-trile per million parts of resin and not more than 0.7 parts of oligomers per 100 parts of resin.
By the term "monovinyl aromatic monomer" is meant a monovinyl aromatic compound having the general Eormula:
Ar-C=CH2 wherein "Ar" represents an aromatic hydrocarbon radical, or an aromatic halohydrocarbon radical of the benzene series, and "R" is hydrogen or the methyl radical.
Examples of such monovinyl aromatic monomers include ll,703B-F -2-.. . --. . , . - .: ... ~ - ., : ~ .
- - ~
5~
styrene, ortho-methylstyrene, meta-methylstyrene, para--methylstyrene, ar-ethylstyrene, ar-vinylxylene, ar--chlorostyrene, and ar-bromostyrene.
Polymers in accordance with the present inven-tion are readily prepared employing monomers of commer-cial purity. Similarly, catalysts and solvents of com-mercial purity are also satisfactory. If it is desired to obtain a polymer of generally uniform composition, it is desirable to either control the monomer composition, that is, the ratio of the monovinylaromatic monomer to the acrylonitrile or to employ known polymerization tech-niques. In carrying out a polymerization in accordance with the present invention, it is essential that the temperature of the polymerization be maintained in excess of 80C and below about 180C during conversion of a major amount of the monomer to polymer. Beneficially, the temperature is maintained between 110C and 150C.
If temperatures lower than the foregoing are employed, generally undesirable conversion rates are obtained and the molecular weight of the product tends to be higher than that desirable for easily fabricated resins. Gen-erally, if the temperature is in excess of the upper limits hereinbefore set forth, undesirably low molecular weight resins are obtained and temperature control of the process becomes quite difficult. During the terminal portion of the polymerization, it is sometimes desirable to employ higher temperatures. Generally, devolatiliza-tion of the polymerization mixture is done at temperatures of 200 to 260C.
17,703B-F -3-10~3S!~
It is desirable to maintain a rate of conversion of at least 20 percent per hour and beneficially under 200 percent per hourO If rates exceed 200 percent per hour, control of the reaction is difficu1t. It is usually desirable to at least initiate polymerization as a mass - or solvent polymerization system in order to maintain a reaction mass having a sufficiently low viscosity that adequate heat transfer can be maintained and r~duce the energy required to agitate or pump the reaction mixture.
The reaction may be completed in a mass or solution system or completed in a suspension system. Usually such solvents are employed at levels up to 50 percent of the reactor contents, however, for most applications it is desirable to maintain a solvent level from 5 to 20 percent by weight. A wide variety of solvents may be employed, however, particularly desirable for polymers containing less than 50 weight percent acrylonitrile is ethylbenzene and for those polymers containing over 50 weight percent acrylonitrile, methylethyl ketone can be employed with benefit. Other solvents which are useful include: cyclohexanone, dimethylformamide, and dimethyl-sulfoxide.
Polymerization in accordance with the present invention is readily carried out employing the conventional reactors which are suitable for the preparation of styrene acrylonitrile resins. Stirred tube stratifying polymeri-zers, recirculating coil polymerizers, so-called boiling reactors, where cooling is obtained by condensing monomer vapor, are all used with benefit.
17,703B-F -4-lOq3~96 Polymerization critically is initiated using an initiator having a half-life of one hour at a tempera-ture between 80C and 180C. Suitable initiators for the practice of the present invention include, for example, s 1 hour 1/2 Life Temperature C
~auroyl Peroxide 80 Decanoyl Peroxide 80 Azobisisobutyronitrile 85 t-Butyl Peroctoate 92 Benzoyl Peroxide 91 t-Butyl Perbenzoate 125 t-Butyl Peracetate 120 l,l-Bis(Di-t-Butylperoxy)-Cyclohexane 115 4-Methyl,l,l-Bis(Di-t-Butyl-peroxy)Cyclohexane 115 Di-t-Butyl Peroxide 149 Diphenyl, di-t-butyl Peroxy Silane 156 Dimethyl, di-t-butyl Peroxy Silane 180 ~,a' Di-t-butyl Peroxy 1,4 Di-isopropyl-Benzene 137 Bis(t-Butyl Peroxy)-3,3,5 Trimethyl Cyclohexane 112 Di-amyl Peroxide 135 .
In order that the desirable characteristics be obtained and polymers be prepared in accordance with the-present invention, the ratio of initiator induced polymeriza-tion . .
17,703B-F -5-lOq3596 initiation to thermally induced polymerization initiation should be in excess of 1.3 and preferably in the range of 2 to 10. The ratio of initiator induced polymerization initiation to thermally induced polymerization initiation for the purposes of the foregoing is considered to be the rate of conversion at a given temperature employing catalyst divided by the rate of polymerization of a like system wherein catalyst or initiator has been omitted.
If there iR excess of thermally produced polymerization initiation, a thermally unstable or less stable polymer composition is produced.
Oligomers are formed during the copolymerization of styrene with acrylonitrile. They are believed to be compounds having the general formula AXSy where:
A represents an acrylonitrile unit, S represents a sty-rene unit, and x and y are integers each having the values 0, 1, 2 or 3, although at present, all such combinations of x and y are not known. The molecular weight of these oligomers range between 157 and 312. During the thermally initated copolymerization of styrene with acrylonitrile, the oligomers typically account for about 1.5 weight percent of the polymer formed. The presence of these oligomers in the polymeric material is generally highly undesirable since they cause a reduction in heat distor-tion temperature; and they are thermally unstable, yield-ing acrylonitrile under conditions typically used for fabricating useful articles out of the polymers~ Their presence in the polymers is detectable using gas-liquid chromatography from which a quantitative analysis may 17,703B-F -6-. .
iO~3S96 be made. The present invention minimizes oligomer content o~ the product.
The following examples further illustrate the invention.
Example 1 A recirculating coil reactor is fed a stream consisting of 75 parts by weight styrene, 25 parts by weight acrylonitrile, 15 parts by weight ethylbenzene, 350 parts per million based on the combined weight of styrene, acrylonitrile and ethylbenzene of bis(ditertiary-butylperoxy)cyclohexane and 500 parts per million based on the combined weight of styrene acrylonitrile and ethylbenzene of n-butyl-mercaptan. The temperature of the feedstream is about 20C. The recirculating coil reactor and contents were maintained at a temperature of 130C and recirculated at a rate of about 1.6 coil volumes per minute. The reactor is operated hydraulically full and under a pressure of about 150 PSIG (10.5 kg/sq cm).
Effluent was re ved from the coil at about 50 weight percent solids and passed to a continuous devolatilizer operating under pressure of about 325 millimeters of mercury absolute. The stream was subsequently passed to a second devolatilizer operating at a temperature of 245C and a pressure of about 30 millimeters of mercury absolute. The lecular weight was determined by gel permeation chromatography employing a polystyrene standard a~ set forth in K. H. Altgelt and J. C. Moore, Polymer Fxactionation, edited by M. J. R. Cantow, Chapter B.4, ~ Academic Press 1967, and had an averaqe molecular weight .. ' ' ' ' 17,703B-F -7-. .
lOq3S96 of 150,000. The polymer contained about 36 parts per million of acrylonitrile and had an oligomer content of 0.1 percent as determined using a gas-liquid chroma-tograph. The polymer was evaluated for thermal stability by placing one gram of the polymer in a glass tube and sealing the tube under a pressure of about 20 millimeters of merc~ry absolute. The sealed tube was then placed in a Wood's metal ~ath at 27~C for about one hour.
At the end of an hour, the sealed tube was removed from the bath, cooled to room temperature and the contents analyzed for acrylonitrile monomer using a gas~ uid chromatograph, 35 parts per million of acrylonitrile and an oligomer content of 0.1 percent were indicated showing essentially no increase in acrylonitrile under temperature conditions approximating those encountered in an injection molding machine. The Vicat heat distor-tion temperature of the polymer was dete~mined on a com-pression molded sample, the value was 113C. When the foregoing procedure was repeated with the exception that lS00 parts per million of a-methylstyrene dimer was employed in place of the 500 parts per million of n-butyl-mercaptan, the molecular weight of the polymer obtained was 190,000 molecular weight units. The polymer contained -50 part9 per million of acrylonitrile. A sample of the polymer was heated for one hour at 275C in a sealed glass tube, was later analyzed to show an acrylonitrile level of 58 parts per million, an increase of acryloni-trile content of 16 percent and an oligomer content of 1/2 percent.
17,703B-F -8-~ . .
l~q3596 For comparative purposes, a third polymerization was carried out wherein the peroxy compound and ~-methyl-styrene dimer and n-butylmercaptan were omitted. The polymerization was carried out at a temperature of 155C.
The polymer had a molecular weight of 190,000 molecular weight units and contained 50 parts per million acryloni-trile and 1.5 weight percent oligomer. A sample was subjected to one hour at 275C under a pressure of 20 ~-millimeters of mercury absolute in a sealed glass tube and was subsequently analyzed by gas-liquid chromato-graphy to indicate an acrylonitrile content of 150 parts per million, an increase of about 200 percent.
Exam~le 2 A series of polymerizations were carried out wherein various mixtures of styrene-acrylonitrile and ethylbenzene were polymerized. In two instances the styrene and acrylonitrile were polymerized in the presence of a polybutadiene rubber and mineral oil. Polymeriza-tions were carried out using a large coil reactor, a small coil reactor, ebulliently cooled reactor, a stirred plug-flow reactor and polymerization in an ampule. With the exception of the ampule polymerizations, all were carried out using continuous feed and continuous take-away of the product. With the exception of the stirred plug--flow reactor, all polymerizations were carried out at the indicated temperature. In the stirred plug-flow reactor polymerization temperature varied between the indicated limits wherein the low temperature was a tem-perature of the first polymerization zone and the highest 17,703B-F -9-.
~3596 temperature was the temperature of the ninth polymeriza-tion zone. The temperatures of zones 2 through 8 were progressively increasing. The percent solids is deter-mined on the effluent from the polymerizer prior to devolatilization of about 200C under a pressure of l millimeter of mercury absolute over a period of 30 min-utes. The polymerization rate as expressed in percent conversion per hour is o~tained by dividing the percent solids by the number of hours or fraction of an hour required for polymerization. Additives are shown as either weight percent or parts per million by weight.
m e polymerization schedules and compositions are set forth in Table 1.
C-17,703B-F -10-.: - .:, ..... - . .. - .. ,..... , :- .. . . .. :
~ c~
U~ ~ ~ o o ~ o ~ I
a~ ~ O O
~ O I I o u~In O CO O O
.~ ~
.,, s~ _, ~ ~ ~ a ~ I u~ O I u~ I I I I I
~ I æ ~m ~
~ r~
.,, _I oP ~a~ o o~ ~ ~ ~ x er ~ ~ ~r o O ~ ~ ~ u~
o~
.,1~r c n ~o ~ o o ~D O O O O O
U~ ~ ~
~ ~E~
~ C~ o o o o ~ o ~ o o o ~r o E~ _ m O O
~ W ~
O ~ ~3 U) t~ O O O~ O ~ O 00 Il~ :' Z ~1 , ~ o o a~
This invention provides an improved acrylonitrile resin which is easily fabricated, has improved thermal stability and a low extractable acrylonitrile content. ~-It further provides an improved process for the preparation of --monovinyl aromatic monomer-acrylonitrile copolymer resins which are thermally stable at injection molding temperatures, and which permits high conversion rates, and provides a resin having high heat distortion temperatures and a low acrylonitrile content, both before and after fabrication.
These benefits and other advantages in accordance with the present invention are achieved in a monovinyl aromatic mcnomer-acrylonitrile copolymer comprising from 9S to 25 parts by weight of a monovinyl aromatic monomer, from 5 to 75 parts by weight of acrylonitrile, the copolymer having a weight average of from 50,000 to 300,000 molecular weight units as determined by gel permeation chromatography employing a polystyrene standard, the copolymer containing not more than 7.5 x 10 5 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 3 parts by weight per part of copolymer of oligomers of styrene and acrylonitrile and characterized in that the polymer is prepared by mass polymerization at a temperature in excess of 80C.
Also within the scope of the present invention is a method fbr the preparation of a monovinyl aromatic monomer-acrylonitrile copolymer containing not more than 7.5 x 10 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 parts by weight, per part of co-polymer, of oligomers of styrene and acrylonitrile by providing a poly-merizable stream comprising from 5 to 75 parts by weight of L~
~ .:
~0'73~j9~
acrylonitrile and from 95 to 25 parts by weight of a monovinyl aromatic monomer, characterized in that the the stream contains from 5 X lO 5 to l X lO 2 parts by weight per part by weight of the polymerizable stream of a free radical initiating catalyst having a half-life of about one hour at a temperature in the range of 80C
to 180C, and maintaining the stream at a polymerization temperature sufficient to cause at least from 20 to 200 percent conversion of the monomer to polymer per hour.
Also within the scope of the present invention is an injection molded monovinyl aromatic monomer-acrylo-nitrile copolymer article, the article having as a princi-pal component thereof a mass-polymerized copolymer of from 5 to 75 parts by weight of acrylonitrile and from 95 to 25 parts by weight of alkenyl aromatic resinous monomer copolymerized therewith, and characterized by containing not more than 75 parts of residual acryloni-trile per million parts of resin and not more than 0.7 parts of oligomers per 100 parts of resin.
By the term "monovinyl aromatic monomer" is meant a monovinyl aromatic compound having the general Eormula:
Ar-C=CH2 wherein "Ar" represents an aromatic hydrocarbon radical, or an aromatic halohydrocarbon radical of the benzene series, and "R" is hydrogen or the methyl radical.
Examples of such monovinyl aromatic monomers include ll,703B-F -2-.. . --. . , . - .: ... ~ - ., : ~ .
- - ~
5~
styrene, ortho-methylstyrene, meta-methylstyrene, para--methylstyrene, ar-ethylstyrene, ar-vinylxylene, ar--chlorostyrene, and ar-bromostyrene.
Polymers in accordance with the present inven-tion are readily prepared employing monomers of commer-cial purity. Similarly, catalysts and solvents of com-mercial purity are also satisfactory. If it is desired to obtain a polymer of generally uniform composition, it is desirable to either control the monomer composition, that is, the ratio of the monovinylaromatic monomer to the acrylonitrile or to employ known polymerization tech-niques. In carrying out a polymerization in accordance with the present invention, it is essential that the temperature of the polymerization be maintained in excess of 80C and below about 180C during conversion of a major amount of the monomer to polymer. Beneficially, the temperature is maintained between 110C and 150C.
If temperatures lower than the foregoing are employed, generally undesirable conversion rates are obtained and the molecular weight of the product tends to be higher than that desirable for easily fabricated resins. Gen-erally, if the temperature is in excess of the upper limits hereinbefore set forth, undesirably low molecular weight resins are obtained and temperature control of the process becomes quite difficult. During the terminal portion of the polymerization, it is sometimes desirable to employ higher temperatures. Generally, devolatiliza-tion of the polymerization mixture is done at temperatures of 200 to 260C.
17,703B-F -3-10~3S!~
It is desirable to maintain a rate of conversion of at least 20 percent per hour and beneficially under 200 percent per hourO If rates exceed 200 percent per hour, control of the reaction is difficu1t. It is usually desirable to at least initiate polymerization as a mass - or solvent polymerization system in order to maintain a reaction mass having a sufficiently low viscosity that adequate heat transfer can be maintained and r~duce the energy required to agitate or pump the reaction mixture.
The reaction may be completed in a mass or solution system or completed in a suspension system. Usually such solvents are employed at levels up to 50 percent of the reactor contents, however, for most applications it is desirable to maintain a solvent level from 5 to 20 percent by weight. A wide variety of solvents may be employed, however, particularly desirable for polymers containing less than 50 weight percent acrylonitrile is ethylbenzene and for those polymers containing over 50 weight percent acrylonitrile, methylethyl ketone can be employed with benefit. Other solvents which are useful include: cyclohexanone, dimethylformamide, and dimethyl-sulfoxide.
Polymerization in accordance with the present invention is readily carried out employing the conventional reactors which are suitable for the preparation of styrene acrylonitrile resins. Stirred tube stratifying polymeri-zers, recirculating coil polymerizers, so-called boiling reactors, where cooling is obtained by condensing monomer vapor, are all used with benefit.
17,703B-F -4-lOq3~96 Polymerization critically is initiated using an initiator having a half-life of one hour at a tempera-ture between 80C and 180C. Suitable initiators for the practice of the present invention include, for example, s 1 hour 1/2 Life Temperature C
~auroyl Peroxide 80 Decanoyl Peroxide 80 Azobisisobutyronitrile 85 t-Butyl Peroctoate 92 Benzoyl Peroxide 91 t-Butyl Perbenzoate 125 t-Butyl Peracetate 120 l,l-Bis(Di-t-Butylperoxy)-Cyclohexane 115 4-Methyl,l,l-Bis(Di-t-Butyl-peroxy)Cyclohexane 115 Di-t-Butyl Peroxide 149 Diphenyl, di-t-butyl Peroxy Silane 156 Dimethyl, di-t-butyl Peroxy Silane 180 ~,a' Di-t-butyl Peroxy 1,4 Di-isopropyl-Benzene 137 Bis(t-Butyl Peroxy)-3,3,5 Trimethyl Cyclohexane 112 Di-amyl Peroxide 135 .
In order that the desirable characteristics be obtained and polymers be prepared in accordance with the-present invention, the ratio of initiator induced polymeriza-tion . .
17,703B-F -5-lOq3596 initiation to thermally induced polymerization initiation should be in excess of 1.3 and preferably in the range of 2 to 10. The ratio of initiator induced polymerization initiation to thermally induced polymerization initiation for the purposes of the foregoing is considered to be the rate of conversion at a given temperature employing catalyst divided by the rate of polymerization of a like system wherein catalyst or initiator has been omitted.
If there iR excess of thermally produced polymerization initiation, a thermally unstable or less stable polymer composition is produced.
Oligomers are formed during the copolymerization of styrene with acrylonitrile. They are believed to be compounds having the general formula AXSy where:
A represents an acrylonitrile unit, S represents a sty-rene unit, and x and y are integers each having the values 0, 1, 2 or 3, although at present, all such combinations of x and y are not known. The molecular weight of these oligomers range between 157 and 312. During the thermally initated copolymerization of styrene with acrylonitrile, the oligomers typically account for about 1.5 weight percent of the polymer formed. The presence of these oligomers in the polymeric material is generally highly undesirable since they cause a reduction in heat distor-tion temperature; and they are thermally unstable, yield-ing acrylonitrile under conditions typically used for fabricating useful articles out of the polymers~ Their presence in the polymers is detectable using gas-liquid chromatography from which a quantitative analysis may 17,703B-F -6-. .
iO~3S96 be made. The present invention minimizes oligomer content o~ the product.
The following examples further illustrate the invention.
Example 1 A recirculating coil reactor is fed a stream consisting of 75 parts by weight styrene, 25 parts by weight acrylonitrile, 15 parts by weight ethylbenzene, 350 parts per million based on the combined weight of styrene, acrylonitrile and ethylbenzene of bis(ditertiary-butylperoxy)cyclohexane and 500 parts per million based on the combined weight of styrene acrylonitrile and ethylbenzene of n-butyl-mercaptan. The temperature of the feedstream is about 20C. The recirculating coil reactor and contents were maintained at a temperature of 130C and recirculated at a rate of about 1.6 coil volumes per minute. The reactor is operated hydraulically full and under a pressure of about 150 PSIG (10.5 kg/sq cm).
Effluent was re ved from the coil at about 50 weight percent solids and passed to a continuous devolatilizer operating under pressure of about 325 millimeters of mercury absolute. The stream was subsequently passed to a second devolatilizer operating at a temperature of 245C and a pressure of about 30 millimeters of mercury absolute. The lecular weight was determined by gel permeation chromatography employing a polystyrene standard a~ set forth in K. H. Altgelt and J. C. Moore, Polymer Fxactionation, edited by M. J. R. Cantow, Chapter B.4, ~ Academic Press 1967, and had an averaqe molecular weight .. ' ' ' ' 17,703B-F -7-. .
lOq3S96 of 150,000. The polymer contained about 36 parts per million of acrylonitrile and had an oligomer content of 0.1 percent as determined using a gas-liquid chroma-tograph. The polymer was evaluated for thermal stability by placing one gram of the polymer in a glass tube and sealing the tube under a pressure of about 20 millimeters of merc~ry absolute. The sealed tube was then placed in a Wood's metal ~ath at 27~C for about one hour.
At the end of an hour, the sealed tube was removed from the bath, cooled to room temperature and the contents analyzed for acrylonitrile monomer using a gas~ uid chromatograph, 35 parts per million of acrylonitrile and an oligomer content of 0.1 percent were indicated showing essentially no increase in acrylonitrile under temperature conditions approximating those encountered in an injection molding machine. The Vicat heat distor-tion temperature of the polymer was dete~mined on a com-pression molded sample, the value was 113C. When the foregoing procedure was repeated with the exception that lS00 parts per million of a-methylstyrene dimer was employed in place of the 500 parts per million of n-butyl-mercaptan, the molecular weight of the polymer obtained was 190,000 molecular weight units. The polymer contained -50 part9 per million of acrylonitrile. A sample of the polymer was heated for one hour at 275C in a sealed glass tube, was later analyzed to show an acrylonitrile level of 58 parts per million, an increase of acryloni-trile content of 16 percent and an oligomer content of 1/2 percent.
17,703B-F -8-~ . .
l~q3596 For comparative purposes, a third polymerization was carried out wherein the peroxy compound and ~-methyl-styrene dimer and n-butylmercaptan were omitted. The polymerization was carried out at a temperature of 155C.
The polymer had a molecular weight of 190,000 molecular weight units and contained 50 parts per million acryloni-trile and 1.5 weight percent oligomer. A sample was subjected to one hour at 275C under a pressure of 20 ~-millimeters of mercury absolute in a sealed glass tube and was subsequently analyzed by gas-liquid chromato-graphy to indicate an acrylonitrile content of 150 parts per million, an increase of about 200 percent.
Exam~le 2 A series of polymerizations were carried out wherein various mixtures of styrene-acrylonitrile and ethylbenzene were polymerized. In two instances the styrene and acrylonitrile were polymerized in the presence of a polybutadiene rubber and mineral oil. Polymeriza-tions were carried out using a large coil reactor, a small coil reactor, ebulliently cooled reactor, a stirred plug-flow reactor and polymerization in an ampule. With the exception of the ampule polymerizations, all were carried out using continuous feed and continuous take-away of the product. With the exception of the stirred plug--flow reactor, all polymerizations were carried out at the indicated temperature. In the stirred plug-flow reactor polymerization temperature varied between the indicated limits wherein the low temperature was a tem-perature of the first polymerization zone and the highest 17,703B-F -9-.
~3596 temperature was the temperature of the ninth polymeriza-tion zone. The temperatures of zones 2 through 8 were progressively increasing. The percent solids is deter-mined on the effluent from the polymerizer prior to devolatilization of about 200C under a pressure of l millimeter of mercury absolute over a period of 30 min-utes. The polymerization rate as expressed in percent conversion per hour is o~tained by dividing the percent solids by the number of hours or fraction of an hour required for polymerization. Additives are shown as either weight percent or parts per million by weight.
m e polymerization schedules and compositions are set forth in Table 1.
C-17,703B-F -10-.: - .:, ..... - . .. - .. ,..... , :- .. . . .. :
~ c~
U~ ~ ~ o o ~ o ~ I
a~ ~ O O
~ O I I o u~In O CO O O
.~ ~
.,, s~ _, ~ ~ ~ a ~ I u~ O I u~ I I I I I
~ I æ ~m ~
~ r~
.,, _I oP ~a~ o o~ ~ ~ ~ x er ~ ~ ~r o O ~ ~ ~ u~
o~
.,1~r c n ~o ~ o o ~D O O O O O
U~ ~ ~
~ ~E~
~ C~ o o o o ~ o ~ o o o ~r o E~ _ m O O
~ W ~
O ~ ~3 U) t~ O O O~ O ~ O 00 Il~ :' Z ~1 , ~ o o a~
2 ~ _ ~ ~ , ,, ~ ~nIn~D,~ u~ , ,, E~ ~ r aJ ~ U~00 0 0 1` ~ ~ O ~ o r~7 m a~ ~
E~u~ ~u~ u~er u~ o~ ~ ~D~1 ~ er ~ In ~ ~a co co P~ _ o ~1 ~ a~
Q~
~;
~; o I~
o , O. o o o oao c~ o o o o o o u~ ~O
~1 ~ ~ ~ ~ ~ ~ ~ o ~ ~r ~ ~ ~ Ln ~r o ~ ,, _l,. .. . . . ... . . . .
o o o o o o o o o o o o o o U~ U~~ o o o U~ Ul ~ o ' ~ ~ ~ ~ t~
~n ~ Ql _ ~ ~ ~ ~ _ ~ ~ c~ u o u ~ Q m u ~ ~ m o m m m m m m m m m a .~, m ~rl U~ O U~
N
h~
X ,~ ~ I~ CO cr~ o ~ ~ , 17, 703B-F
~07359 dP
o ~ o CO o .~ ~
.,1 h ,a a~ s~
a)~
~: Q Q o I I I I
r~
P; d~
U~
~Q ~ C~ o ~o o O ~D ~r ~ ~ ~
U~
0'~
.,1 o ~~r ~o ~ .
~ ~ U~
CQ ~ ~ ~
~ , ,.
_ ~ ~ ~ o CO
m ,1 0 0 ~ O
~ia) ~ ~
~;X ~ ~ CO C5'~ CO er ~ ~,~ ~ o ~ oo O n ~ ~ er u~ ~
~ ~ ~ o ~ ~î . ~
S~ ' al c~ a x E~ ~ V D
I ~ u~
~1 ~ ~
o a) ~1 ~1 _I _I ~1 ~E~
~ I I 1 5 s ,~ a ~ ~ I I I I I
c~ ~; I I ~ I I
_ ~ ~P coco o ~1 o~
~ O
~ U~
17, 703B-F -12-.,. . .. - : ~ ~ ~- .
lOq3596 o E~ _ m m a~
~a a~ ~
o o ~0 u o m ~ ~
O N a~
~ N ~ 3 ~ o o m ~ a a~ o o o _l -- s~ O ~
R
m ~ I a) o ~ h 1 ~ ~ N
a~ ~ x u~ X a) rl-rl O ~1 0 ~ O O
rl .q t ~1 ~ h S-lC~ C) ~1) a.~ ~ E-~
~1 1 ~ N
O ~ C ~I 11 11 11 11~ ~ .
~d R o ~ a) ~I tJ`,~
~ _ _ _ _ _ _ 17,703B--F
" , . .. . . .. . ..
-10~3596 It should be noted that Examples l through 2 are within the scope of the present invention. The remaining examples are provided for comparative purposes only. The amount of acrylonitrile copolymerized in the product was determined and the volatile materials such as ethylbenzene styrene dimers and trimers were also determined. In most cases, the weight average and number average molecular weight were determined and in four instances the solution viscosity was determined which is a solution of lO weight percent polymer in methylethyl ketone at 25~C. Vicat heat distortion was determined on all polymers. The residual acrylonitrile was deter-mined before and after thermal stability testing in the manner of Example l. The results are set forth in Table 2.
17,703B-F -14-1(37359~i a a ,~
.,, s~
S~ O ~ a: ~ ~ ~ ~ o u~ er O ~ 00 CO ~1 a~ ~ In o H ~ ~
O d~
C~
~ a~ ~ _I ~ oo In ~ o a~ co ~ ~ ~7 er ~ a~
-.
m ,~1 aJ. O ~ a~ ~ o~ ~ a~ ~r ~7 oo ~ ~D CO C~ r~ er O ~; ~ ~ _l ~ ~ ~ ~ In ~ I~
E~ a . m Z u~
~ ~ o ~ ~ ~ ~ ~ o o ':~ ' ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ _ ~
o , tn u~
0~1'0 X O ,,~
~4 U~ ~`
U~ _ o O O O t~ o o o o O O
t:l ~ ooooooooo,~¢,¢ooo @ ~ ~ i ~ O' c~ a~ Z ~ `
~ . ~1 0 00 ~ co o ~ . .
~ ~ _ O O O O O O O O O O O O
2i O ~ O O O O O O O O O l¢ ¢ O O O
_I _ O O O O O O O O O Z Z O O O
_ ;~i O ~ o 1~1 . .
E~ ~
~ ~ ~ r~ u~ o ~ ~ o~ ~ ~ ~ ~r ~ r~ o e u~ ~ O O O O ~ O ,, bq ~ O o o O O O O O O o O O
_l ~ tn _i ~ ~ o ~ C~ _I O _I O O U~ O O
~a ql oo~1ooooooooooo ,1 e ~n .~ oooooooooooooo m ~ ~ r ~ o o O O O ~
~;d E~ ~1ooooooooooo E~ u~ . . . . . . . . . . .
. o o O O O o O o O O O O O O
J~
E~u~ ~u~ u~er u~ o~ ~ ~D~1 ~ er ~ In ~ ~a co co P~ _ o ~1 ~ a~
Q~
~;
~; o I~
o , O. o o o oao c~ o o o o o o u~ ~O
~1 ~ ~ ~ ~ ~ ~ ~ o ~ ~r ~ ~ ~ Ln ~r o ~ ,, _l,. .. . . . ... . . . .
o o o o o o o o o o o o o o U~ U~~ o o o U~ Ul ~ o ' ~ ~ ~ ~ t~
~n ~ Ql _ ~ ~ ~ ~ _ ~ ~ c~ u o u ~ Q m u ~ ~ m o m m m m m m m m m a .~, m ~rl U~ O U~
N
h~
X ,~ ~ I~ CO cr~ o ~ ~ , 17, 703B-F
~07359 dP
o ~ o CO o .~ ~
.,1 h ,a a~ s~
a)~
~: Q Q o I I I I
r~
P; d~
U~
~Q ~ C~ o ~o o O ~D ~r ~ ~ ~
U~
0'~
.,1 o ~~r ~o ~ .
~ ~ U~
CQ ~ ~ ~
~ , ,.
_ ~ ~ ~ o CO
m ,1 0 0 ~ O
~ia) ~ ~
~;X ~ ~ CO C5'~ CO er ~ ~,~ ~ o ~ oo O n ~ ~ er u~ ~
~ ~ ~ o ~ ~î . ~
S~ ' al c~ a x E~ ~ V D
I ~ u~
~1 ~ ~
o a) ~1 ~1 _I _I ~1 ~E~
~ I I 1 5 s ,~ a ~ ~ I I I I I
c~ ~; I I ~ I I
_ ~ ~P coco o ~1 o~
~ O
~ U~
17, 703B-F -12-.,. . .. - : ~ ~ ~- .
lOq3596 o E~ _ m m a~
~a a~ ~
o o ~0 u o m ~ ~
O N a~
~ N ~ 3 ~ o o m ~ a a~ o o o _l -- s~ O ~
R
m ~ I a) o ~ h 1 ~ ~ N
a~ ~ x u~ X a) rl-rl O ~1 0 ~ O O
rl .q t ~1 ~ h S-lC~ C) ~1) a.~ ~ E-~
~1 1 ~ N
O ~ C ~I 11 11 11 11~ ~ .
~d R o ~ a) ~I tJ`,~
~ _ _ _ _ _ _ 17,703B--F
" , . .. . . .. . ..
-10~3596 It should be noted that Examples l through 2 are within the scope of the present invention. The remaining examples are provided for comparative purposes only. The amount of acrylonitrile copolymerized in the product was determined and the volatile materials such as ethylbenzene styrene dimers and trimers were also determined. In most cases, the weight average and number average molecular weight were determined and in four instances the solution viscosity was determined which is a solution of lO weight percent polymer in methylethyl ketone at 25~C. Vicat heat distortion was determined on all polymers. The residual acrylonitrile was deter-mined before and after thermal stability testing in the manner of Example l. The results are set forth in Table 2.
17,703B-F -14-1(37359~i a a ,~
.,, s~
S~ O ~ a: ~ ~ ~ ~ o u~ er O ~ 00 CO ~1 a~ ~ In o H ~ ~
O d~
C~
~ a~ ~ _I ~ oo In ~ o a~ co ~ ~ ~7 er ~ a~
-.
m ,~1 aJ. O ~ a~ ~ o~ ~ a~ ~r ~7 oo ~ ~D CO C~ r~ er O ~; ~ ~ _l ~ ~ ~ ~ In ~ I~
E~ a . m Z u~
~ ~ o ~ ~ ~ ~ ~ o o ':~ ' ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ _ ~
o , tn u~
0~1'0 X O ,,~
~4 U~ ~`
U~ _ o O O O t~ o o o o O O
t:l ~ ooooooooo,~¢,¢ooo @ ~ ~ i ~ O' c~ a~ Z ~ `
~ . ~1 0 00 ~ co o ~ . .
~ ~ _ O O O O O O O O O O O O
2i O ~ O O O O O O O O O l¢ ¢ O O O
_I _ O O O O O O O O O Z Z O O O
_ ;~i O ~ o 1~1 . .
E~ ~
~ ~ ~ r~ u~ o ~ ~ o~ ~ ~ ~ ~r ~ r~ o e u~ ~ O O O O ~ O ,, bq ~ O o o O O O O O O o O O
_l ~ tn _i ~ ~ o ~ C~ _I O _I O O U~ O O
~a ql oo~1ooooooooooo ,1 e ~n .~ oooooooooooooo m ~ ~ r ~ o o O O O ~
~;d E~ ~1ooooooooooo E~ u~ . . . . . . . . . . .
. o o O O O o O o O O O O O O
J~
3 ~ o O O O O O O O O O er ~1 ~I O O
~ ~ O o o o O' o O O O o o o O o rl ~
~i!; O ~ I~ O Inu~ ~ ~ o u~ u~ In In U'~ .
1~ :
~ O _I N ~ ~r U) U~ I` X a~ O _I ~ ~ ~r 1~3 Z
1`/, 703B-F -15-.
' ' ' . '' .
.
a) ..
a ,, .,, s~
U o ~ CO ~ o ~ ~ ~D ~ ~ r~ In ' ~1 H ct~ 11~ t~l ~r ~ ~P
_l ~1 .
~ S~ ~ CO O ~ In O l~q _l ~ Q-Q
h m ~ ~ ,1 a) o ~ul O u, a~ o :~
O ~; 4~ ~ ~ ~P er ~
E~ ~ Q C
æ ~ x o ~ ~ ~ . . U~
1:~ (~ o t~ N 0~ Cl _I --p:; t) t`J
O .,~ .
.~ ~ o a ~ .
-~ o tn ~ o -,, ,o : ~ . O O o ~Y
. ~ . ,4 ~ O O O
'. ~ ~,: ~: Z ~ ~ ~ Z
C)--I o o o _I
o O o _~ ~ ~¢ O O O t¢ .
~ ~ ~ Z ~ ~r co Z ~ _ ~ .
h o D ~ C E~
1~1 ~n C
~ ~ o~ S ,s:: C ~ ' a~ D ~ ~ ~ ~ ~
P~ ~1 u~ E~ ,~ 3 ~ ~ o ~ ~ ~ s~ 'O~ Q~' :1 ~ ~_I o O o ~a a~ o o o o o ~1 E~
Ul ,1 oo oo o U U 4 ~1~ a ~ o :q~ ~ o o o Q
1;op ~ OO OO O
E~u~ .. .. . o oo oo o a~
3: ~ ~
_~ o o o o 5.1 ~ O C
m o O o o o ~ ;, .,, ~: O dP ~
~ CO00 ~ ~ o ~ tJ' ~ U
Z O-IJ 1~t~l O ~1 a~ j tn h F~ S 3 C :~ Q, Q. ~ _ _ _ X O u~ ~ U
~3 Z ~
17, 703B--F -16-In a manner similar to the foregoing illus-trations, other monovinyl aromatic monomers and acrylo-nitrile copolymers are readily copolymerized to provide resins of low oligomer content, high heat stability that is a low tendency to generate acrylonitrile under fabri-cation conditions. Such resins are readily prepared containing from 50 to 75 weight percent acrylonitrile and most beneficially in the ranges of 20 to 35 weight percent acrylonitrile and 50 to 70 weight percent acry-lonitrile.
17,703B-F -17-
~ ~ O o o o O' o O O O o o o O o rl ~
~i!; O ~ I~ O Inu~ ~ ~ o u~ u~ In In U'~ .
1~ :
~ O _I N ~ ~r U) U~ I` X a~ O _I ~ ~ ~r 1~3 Z
1`/, 703B-F -15-.
' ' ' . '' .
.
a) ..
a ,, .,, s~
U o ~ CO ~ o ~ ~ ~D ~ ~ r~ In ' ~1 H ct~ 11~ t~l ~r ~ ~P
_l ~1 .
~ S~ ~ CO O ~ In O l~q _l ~ Q-Q
h m ~ ~ ,1 a) o ~ul O u, a~ o :~
O ~; 4~ ~ ~ ~P er ~
E~ ~ Q C
æ ~ x o ~ ~ ~ . . U~
1:~ (~ o t~ N 0~ Cl _I --p:; t) t`J
O .,~ .
.~ ~ o a ~ .
-~ o tn ~ o -,, ,o : ~ . O O o ~Y
. ~ . ,4 ~ O O O
'. ~ ~,: ~: Z ~ ~ ~ Z
C)--I o o o _I
o O o _~ ~ ~¢ O O O t¢ .
~ ~ ~ Z ~ ~r co Z ~ _ ~ .
h o D ~ C E~
1~1 ~n C
~ ~ o~ S ,s:: C ~ ' a~ D ~ ~ ~ ~ ~
P~ ~1 u~ E~ ,~ 3 ~ ~ o ~ ~ ~ s~ 'O~ Q~' :1 ~ ~_I o O o ~a a~ o o o o o ~1 E~
Ul ,1 oo oo o U U 4 ~1~ a ~ o :q~ ~ o o o Q
1;op ~ OO OO O
E~u~ .. .. . o oo oo o a~
3: ~ ~
_~ o o o o 5.1 ~ O C
m o O o o o ~ ;, .,, ~: O dP ~
~ CO00 ~ ~ o ~ tJ' ~ U
Z O-IJ 1~t~l O ~1 a~ j tn h F~ S 3 C :~ Q, Q. ~ _ _ _ X O u~ ~ U
~3 Z ~
17, 703B--F -16-In a manner similar to the foregoing illus-trations, other monovinyl aromatic monomers and acrylo-nitrile copolymers are readily copolymerized to provide resins of low oligomer content, high heat stability that is a low tendency to generate acrylonitrile under fabri-cation conditions. Such resins are readily prepared containing from 50 to 75 weight percent acrylonitrile and most beneficially in the ranges of 20 to 35 weight percent acrylonitrile and 50 to 70 weight percent acry-lonitrile.
17,703B-F -17-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A monovinyl aromatic monomer-acrylonitrile copolymer comprising from 95 to 25 parts by weight of a monvinyl aromatic monomer, from 5 to 75 parts by weight of acrylonitrile, the copolymer having a weight average of from 50,000 to 300,000 molecular weight units as determined by gel per-meation chromatography employing a polystyrene standard, the copolymer con-taining not more than 7.5 x 10-5 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 3 parts by weight per part of copolymer of oligomers of styrene and acrylonitrile and characterized in that the polymer is prepared by mass polymerization at a temperature in excess of 80°C.
2. The copolymer of claim 1 characterized by containing 20 to 35 parts by weight of acrylonitrile.
3. The copolymer of claim 1 characterized by containing from 50 to 75 parts by weight of acrylonitrile.
4. A method for the preparation of a monovinyl aromatic monomer-acrylonitrile copolymer containing not more than 7.5 x 10 5 parts by weight per part of copolymer of free acrylonitrile and not more than 7 x 10 3 parts by weight, per part of copolymer, of oligomers of styrene and acrylonitrile by providing a polymerizable stream comprising from 5 to 75 parts by weight of acrylonitrile and from 95 to 25 parts by weight of a monovinyl aromatic monomer, characterized in that the stream contains from 5 x 10 to 1 x 10 parts by weight per part by weight of the polymerizable stream of a free radical initiating catalyst having a half-life of about one hour at a temperature in the range of 80°C to 180~C, maintaining the stream at a polymerization temperature sufficient to cause at least from 20 to 200 percent conversion of the monomer to polymer per hour.
5. Method of claim 4 characterized in that the monomer stream contains from about 20 to 35 parts by weight of acrylonitrile.
6. Method of claim 4 characterized in that the polymerizable stream contains from about 50 to 75 parts by weight acrylonitrile.
7. An injection molded monovinyl aromatic monomer-acrylonitrile copolymer article, the article having as a principal component thereof a mass-polymerized copolymer of from 5 to 75 parts by weight of acrylonitrile and from 95 to 25 parts by weight of alkenyl aromatic resinous monomer co-polymer-ized therewith and characterized by containing not more than 75 parts of residual acrylonitrile per million parts of resin and not more than 0.7 parts of oligomers per 100 parts of resin.
8. Article of claim 7 characterized in that the monovinyl aromatic monomer is styrene.
9. Article of claim 7 characterized in that styrene and acrylonitrile are present in a proportion from 50 to 75 parts by weight of acrylonitrile to 50 to 25 parts by weight of styrene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57589275A | 1975-05-08 | 1975-05-08 | |
| US64358675A | 1975-12-22 | 1975-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073596A true CA1073596A (en) | 1980-03-11 |
Family
ID=27076819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA252,056A Expired CA1073596A (en) | 1975-05-08 | 1976-05-07 | Monovinyl aromatic monomer-acrylonitrile copolymer and preparation thereof |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS51136777A (en) |
| AU (1) | AU501419B2 (en) |
| CA (1) | CA1073596A (en) |
| DE (1) | DE2619969C2 (en) |
| FR (1) | FR2310366A1 (en) |
| GB (1) | GB1515975A (en) |
| IT (1) | IT1061260B (en) |
| NL (1) | NL182405C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2809180B2 (en) * | 1978-03-03 | 1980-01-10 | Basf Ag, 6700 Ludwigshafen | Process for the production of copolymers from α-methylstyrene and acrylonitrile |
| JPS5962604A (en) * | 1982-10-01 | 1984-04-10 | Kanegafuchi Chem Ind Co Ltd | Preparation of copolymer |
| JP4679929B2 (en) * | 2005-02-24 | 2011-05-11 | テクノポリマー株式会社 | Infrared transparent thermoplastic resin composition and molded article using the same |
| JP5805066B2 (en) | 2010-03-05 | 2015-11-04 | 日本エイアンドエル株式会社 | Thermoplastic resin composition for vehicle lamp housing |
| JP5807113B2 (en) * | 2011-06-20 | 2015-11-10 | タイ エイビーエス カンパニー リミテッド | Styrene-acrylonitrile resin having improved transparency and method for producing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE787612A (en) * | 1971-08-16 | 1973-02-16 | Monsanto Co | CONTINUOUS MASS POLYMERIZATION PROCESS |
| US3813369A (en) * | 1972-05-25 | 1974-05-28 | Monsanto Co | Continuous mass polymerization process |
| JPS4920076A (en) * | 1972-06-15 | 1974-02-22 | ||
| JPS5236495B2 (en) * | 1972-08-12 | 1977-09-16 |
-
1976
- 1976-04-08 AU AU12808/76A patent/AU501419B2/en not_active Expired
- 1976-05-03 NL NL7604674A patent/NL182405C/en not_active IP Right Cessation
- 1976-05-06 DE DE19762619969 patent/DE2619969C2/en not_active Expired
- 1976-05-07 FR FR7613850A patent/FR2310366A1/en active Granted
- 1976-05-07 JP JP5202976A patent/JPS51136777A/en active Granted
- 1976-05-07 CA CA252,056A patent/CA1073596A/en not_active Expired
- 1976-05-07 GB GB1890776A patent/GB1515975A/en not_active Expired
- 1976-05-07 IT IT4937676A patent/IT1061260B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51136777A (en) | 1976-11-26 |
| AU501419B2 (en) | 1979-06-21 |
| IT1061260B (en) | 1983-02-28 |
| FR2310366A1 (en) | 1976-12-03 |
| DE2619969C2 (en) | 1984-03-15 |
| GB1515975A (en) | 1978-06-28 |
| AU1280876A (en) | 1977-10-13 |
| NL182405C (en) | 1988-03-01 |
| FR2310366B1 (en) | 1979-03-23 |
| DE2619969A1 (en) | 1976-11-18 |
| NL7604674A (en) | 1976-11-10 |
| NL182405B (en) | 1987-10-01 |
| JPS6224443B2 (en) | 1987-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6593424B2 (en) | Method for preparing thermoplastic resin | |
| US3110695A (en) | Process for polymerizing methylmethacrylate in presence of polyethylene oxide | |
| KR100579348B1 (en) | High gloss high impact monovinylidene aromatic polymers | |
| US4068064A (en) | Method for preparing monovinyl aromatic monomer-acrylonitrile copolymer | |
| EP0212700B2 (en) | Styrenic polymer resins having improved flow characteristics | |
| CA1073596A (en) | Monovinyl aromatic monomer-acrylonitrile copolymer and preparation thereof | |
| US5115055A (en) | Hydroperoxide catalyzed free radical polymerization of vinyl aromatic monomers | |
| US4268652A (en) | Color styrene-acrylonitrile polymers | |
| US3189569A (en) | Stabilization of styrene-acrylonitrile polymers with alkyl-substituted phenols and vic-epoxy compounds | |
| US5145924A (en) | Free radical polymerization of styrene monomer | |
| US2739142A (en) | Method of preparation of moldable copolymers of styrene and acrylonitrile | |
| US2646423A (en) | Polymers of alkenyl aromatic compounds and acrylonitrile and method of making the same | |
| US4275182A (en) | Process for the preparation of improved styrene acrylic acid copolymers | |
| KR100874030B1 (en) | Manufacturing method of copolymer of styrene monomer and acrylonitrile monomer | |
| CA1166791A (en) | Preparation of alkenyl aromatic monomer butadiene rubber and preparation of impact resistant resin therefrom | |
| US4100227A (en) | Transparent impact-resistant polystyrene structure | |
| US3325457A (en) | Method of preparing acrylonitrile polymers | |
| US5455321A (en) | Process for producing high molecular weight monovinylidene aromatic polymers | |
| US3201375A (en) | Use of acyl peroxides as catalysts in the preparation of acrylonitrile-styrenealpha-methyl-styrene terpolymers | |
| Priddy et al. | Heat resistant styrene/α‐methylstyrene copolymers made via continuous anionic polymerization at high temperature | |
| KR100548632B1 (en) | Preparing method for transparent resin by bulk polymerization | |
| US2816095A (en) | Terpolymer of methylstyrenes | |
| JPH07116262B2 (en) | Method for producing α-methylstyrene copolymer | |
| US4833223A (en) | High molecular weight polystyrene and method | |
| KR850000111B1 (en) | A process for preparation of alkenyl aromatic-butadien rubbery polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |