CA1088246A - Modification of vinylchloride polymers - Google Patents
Modification of vinylchloride polymersInfo
- Publication number
- CA1088246A CA1088246A CA270,832A CA270832A CA1088246A CA 1088246 A CA1088246 A CA 1088246A CA 270832 A CA270832 A CA 270832A CA 1088246 A CA1088246 A CA 1088246A
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- Canada
- Prior art keywords
- weight
- parts
- copolymer
- vinylchloride
- polymer
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
MODIFICATION OF VINYLCHLORIDE POLYMERS
Abstract of the Disclosure A rubbery-elastic graft copolymer of 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of sty-rene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 µm is prepared by emulsion polymerisation of the monomer mixture in the presence of the copolymer in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsifier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at pH va-lues below 7 and mixed with a vinylchloride polymer to improve impact strength thereof with retention of transparency.
Abstract of the Disclosure A rubbery-elastic graft copolymer of 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of sty-rene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 µm is prepared by emulsion polymerisation of the monomer mixture in the presence of the copolymer in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsifier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at pH va-lues below 7 and mixed with a vinylchloride polymer to improve impact strength thereof with retention of transparency.
Description
8Z~î
This invention relates to the modiflcation of vinylchlo-ride polymers, in particular polyvinylchloride by means of cer-tain rubbery-elastic graft polymers as additive~, for the pur-pose of improving the notched impact strength and reducing the white fracture without spoiling the transparency.
Mixtures of rubbery-elastic graft copolymers and vinyl-chloride polymers are basically known; for example German Au~-lege3chrift No. 1,470,866 discloses ~uitable graft polymers for the modification of polyvinylchloride. These graft polymers are obtained by ~olymerisation of from 80 to 30 part~ by weight of a mixture of from 80 to 30 parts by weight of styrene, from 10 to 45 parts by weight of methylmethacrylate and from 10 to 50 parts by weight of acrylonitrile in the presence of from 20 to 70 parts by weight of polybutadiene, or in the presence of a co-polymer of from 100 to 70 parts by weight of butadiene and of from 0 to 30 parts by weight of styrene. The particle size is from 0.02 to 0.20/um.
The mouldings obtained from mixtures of vinylchloride polymers and these graft polymers have, however, a poor surface quality if the usual methods of processing polyvinylohloride are employed. This difficulty can be overcome only by employlng special homogenising methods. Thus, it is not a praotioable 80-lution to add the necessary addltives suoh as stabill~ers, lu-bricants and rubber-like graft polymers as modlflers to the transparent pulverulent polyvinylchloride and then extrude or blow the mixture to produce moulded articles such as sheets or bottles. The products obtained under these conditions invariably have an unsightly rough surface.
The present invention is based upon the ~inding that rubbery-elastic graft polymers which have been produced by a Le A 16 985r ~ 1 ~
.
1~88Z4~i particular method have all the previously known advantageous effects on vinyl-chloride polymers including the homopolymer, polyvinylchloride, without giving rise t:o poor surface characteristics.
According to one aspect of the invention there is provided a method of modifying a vinylchloride polymer wherein from 98 to 80% by weight of the vinylchloride polymer is mixed with from 2 to 20% by weight of a rubbery-elastic graft copolymer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methyl-methacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average part-icle size of from 0.05 to 0.5 ~m, the graft copolymer having been prepared by emulsion polymerisation of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsifler which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
The invention also relates in another aspect to a modified vinyl-chloride polymer which comprises from 98 to 80~ by weight of vinylohloride polymer mixed with from 2 to 20% by weight of a rubbery-elastic graft copoly-mer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of ac~ylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 ~m, the graft copolymer having been prepared by emulsion polymerisation ~ -2-1088Z~6 of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a per-oxydisulphate and an alkanolamine and of an emulsifier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
In a preferred embodiment of the invention the vinylchloride polymer is polyvinyl chloride homopolymer. In another preferred embodiment of the invention the graft copolymers have an average particle diameter (d50) of from 0.08 to 0.20~um.
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~ -2a-': , ~ ' . ' ,' ' ' 108824~i When the rubbery-elastic copolymers described above are used as modifying agents for increasing the notched impact strength and reducing the white ~racture in vinylchloride polymers, they have no deleterious effect on the transparency ol tlle material, and the mixture ha~ excellent proces~ing properties. In particular, moulded products having smooth and perfect surfaces are obtained by the usual proce~sing techniques employed for vinylchloride polymers.
The particle sizes indicated above ~or the copolymers used as a base for the graft copolymers are necessary for obtaining good transparency. The choice of monomers is substantially determined by the refractive index of the material. In the present case, they are selected to have substantially the same refractive index as polyvinylchloride so that the transparency is preqerved.
Methods of preparing the copolymers which constitute the base of the graft copolymers and the methods of preparing the graft copolymers them elves are already known. In the pre~ent case, the decisive factors which determine whether the graft copolymers can be used as modifying agents for vinylchloride polymers are the correct choice of catalyst and emulsifiers and the correct method of processing. The catalysts used must be a combination of a peroxydisulphate, preferably potassium or ammo-nium peroxydisulphate, and an alkanolamine, preferably trietha-nolamine cr diethanolamine. The porportions of the components of the catalyst are preferably 1:1 and the quantity of catalyst used is preferably from 0.3 to 0.5 % by weight, based on the quantity of reactants.
Suitable emulsifiers include salts of long chain fatty acids or of resinic acids, preferably sodium and potassium salts Le A 16 985 _ 3 _ 10~824~:;
of disproportionated abietic acid (alkylsulphates and alkyl-sulphonates ~re not suitable) or combinations thereof.
The compounds used as electrolytes for precipitation are preferably acids, in particular dilute acetic acid.
If the copolymer which forms the base of the graft co-polymer is required to be cross-linked, the preferred cross-linking monomer is divinylbenzene.
The graft copolymers may be used for modifying any vinyl chloride polymer, but they are particularly envisaged for poly-vinylchloride and copolymers of vinylchloride, in particular with vinylidenechloride, vinyl esters such as vinylacetate, acry-lic acid or methacrylic acid and esters thereof, nitriles and amides, maleic acid derivatives, vinyl ethers and olefinically unsaturated hydrocarbons such as ethylene, propylene and buty-lene.
A product can, of course, be expected to be transparent and colourless only if the refractive index of the vinylchloride polymer correspond~ at least approximately to that of the graft copolymer.
The particular method used for preparing the vinylchlo-rlde polymer is generally immaterial, but the usual emulsion, suspension or solvent-free polymerisation processes can be employed.
Le A 16~ _ 4 _ ,. , ~ ~ .
1088Z4~; `
General metho~ of procedure To test the surface characteristics, pulverulent mixtures were prel)ared from 88 parts by weight of poly-vinylclllori~e, 12 parts by weight of a graft polymer, 1.5 parts by weight of di-n-octyltindithioglycolic acid ester 1.0 part by weight of isotridecylstearate and 0.2 part by weight of montanic acid ester and the mixtures were blow-moulded in a single path extruder to produce tubular films.
The surface quality ol the Iilms was assessed visually.
To test the notched impact strength (DIN 53 453) transparency (expresse~ in terms of the proportion of scattered light by the ASTM Test Method D307) and white fracture (visual assessment), mixtures of 85 parts by weight of polyvinylchloride, 15 parts by weight of a graft polymer, 1.5 parts by weight of di-n-octyltindithioglycolic acid ester and 0.2 part by weight of montanic acid ester were homogenised on rollers at 180C and pressed to form plate~. The polyvinylchloride used was a product with K-value 57 produced by solvent-free polymerisation.
PreParation-of the ~xaft pol~ers Graft base 1 or 2 was introduced in the form of an approximately 50% latex into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and dropping funnels, and sufficient salt-free water was added to ~ ovide a total of 200 parts by weight. 0.01 part by weight of the disodium salt of ethylenediaminotetracetic acid was then introduced, the oxygen was replaced by nitrogen and the reac-tion mixture was heated to 65C~ 0.3 part by weight of potassium 3 peroxydisulphate in 13 parts by weight of water was then Le A 16 985 - 5 _ .
1088Z4~i addcd, lollowcd, in the course of 4 hours, by the monomer mixture, emulsifier, sodium hydroxide solution and triethanolamine. The mixture was then stirred for a further 1~ hours at ~5C and the resulting latex was stabilised with 0.5 part by weight of2,6-di-tertiary butyl-~-cresol dispersed in water.
Graft base l is a copolymer of 73% by weight of butadiene, 25~ by weight of styrene and 2~ by weight of divinylbenzene. It is provided in the form of 45.9~ latex.
The particles have an average diameter (d50) of 0.12 ~m.
Graft base 2 is a copolymer of 70~ by weight of butadiene, 20% by weight of styrene and lO~ by weight of acrylonitrile. Average particle diameter 0.08 pm. The graft base is provided as a 40.2~ latex.
Quantitative proportions and other details concerning the preparation of seven graft polymer latices are summarised in Table l. Lati~es l and 2 are in accordance with the present invention while latices 3 to 7 are com-parison products. Latices l and 2 can easily be precip-itated with 2% acetic acid and then filtered, washed and dried under vacuum Latioes 3 to 7 cannot be worked up in this way and require salt solutions for precipitation, Table 2 shows the properties of mixtures of polyvinyl-chloride and products l to 7. The mixtures were prepared and tested by the methods indicated above.
Table 3 which gives a summary of experiments 8 to lO, shows that precipitation of graft polymer latices with dilute acetic acid is posæible only if the latices contain dialkanolamine as catalyst in addition to peroxydiæulphate.
Precipitation is not possible if other amineæ are uæed.
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Le A 16 98~ -- 8 --1088Z4~i Table 3 : Influence of varlous types of amines Parts by wei~ht Experim nt Experiment Experiment Salt-free water 200.0 200.0 200.0 Graft base 1 50.0 50.0 50.0 Styrene 25.0 25.025,0 , Methylmethacrylate22.5 22.5 22.5 Acrylonitrile 2,5 2.5 2.5 Na salt of disproportion-ated abietic acid 1.5 1.5 1.5 N sodium hydroxide solution 1.25 1.25 1.25 Disodium salt of ethylenediaminotetracetic acid 0.01 0.01 0.01 Potassium peroxydisulphate 0.3 0.3 0.3 Tributylamine 0.37 . - _ Diethylolamine - 0.21 iethylaminoethanol - - 0.24 Precipitation with :: acetic acid l.-Q.~.2~ _ 9 _ .
This invention relates to the modiflcation of vinylchlo-ride polymers, in particular polyvinylchloride by means of cer-tain rubbery-elastic graft polymers as additive~, for the pur-pose of improving the notched impact strength and reducing the white fracture without spoiling the transparency.
Mixtures of rubbery-elastic graft copolymers and vinyl-chloride polymers are basically known; for example German Au~-lege3chrift No. 1,470,866 discloses ~uitable graft polymers for the modification of polyvinylchloride. These graft polymers are obtained by ~olymerisation of from 80 to 30 part~ by weight of a mixture of from 80 to 30 parts by weight of styrene, from 10 to 45 parts by weight of methylmethacrylate and from 10 to 50 parts by weight of acrylonitrile in the presence of from 20 to 70 parts by weight of polybutadiene, or in the presence of a co-polymer of from 100 to 70 parts by weight of butadiene and of from 0 to 30 parts by weight of styrene. The particle size is from 0.02 to 0.20/um.
The mouldings obtained from mixtures of vinylchloride polymers and these graft polymers have, however, a poor surface quality if the usual methods of processing polyvinylohloride are employed. This difficulty can be overcome only by employlng special homogenising methods. Thus, it is not a praotioable 80-lution to add the necessary addltives suoh as stabill~ers, lu-bricants and rubber-like graft polymers as modlflers to the transparent pulverulent polyvinylchloride and then extrude or blow the mixture to produce moulded articles such as sheets or bottles. The products obtained under these conditions invariably have an unsightly rough surface.
The present invention is based upon the ~inding that rubbery-elastic graft polymers which have been produced by a Le A 16 985r ~ 1 ~
.
1~88Z4~i particular method have all the previously known advantageous effects on vinyl-chloride polymers including the homopolymer, polyvinylchloride, without giving rise t:o poor surface characteristics.
According to one aspect of the invention there is provided a method of modifying a vinylchloride polymer wherein from 98 to 80% by weight of the vinylchloride polymer is mixed with from 2 to 20% by weight of a rubbery-elastic graft copolymer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methyl-methacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average part-icle size of from 0.05 to 0.5 ~m, the graft copolymer having been prepared by emulsion polymerisation of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsifler which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
The invention also relates in another aspect to a modified vinyl-chloride polymer which comprises from 98 to 80~ by weight of vinylohloride polymer mixed with from 2 to 20% by weight of a rubbery-elastic graft copoly-mer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of ac~ylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 ~m, the graft copolymer having been prepared by emulsion polymerisation ~ -2-1088Z~6 of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a per-oxydisulphate and an alkanolamine and of an emulsifier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
In a preferred embodiment of the invention the vinylchloride polymer is polyvinyl chloride homopolymer. In another preferred embodiment of the invention the graft copolymers have an average particle diameter (d50) of from 0.08 to 0.20~um.
~ . ''" .
i .
: .:
~ -2a-': , ~ ' . ' ,' ' ' 108824~i When the rubbery-elastic copolymers described above are used as modifying agents for increasing the notched impact strength and reducing the white ~racture in vinylchloride polymers, they have no deleterious effect on the transparency ol tlle material, and the mixture ha~ excellent proces~ing properties. In particular, moulded products having smooth and perfect surfaces are obtained by the usual proce~sing techniques employed for vinylchloride polymers.
The particle sizes indicated above ~or the copolymers used as a base for the graft copolymers are necessary for obtaining good transparency. The choice of monomers is substantially determined by the refractive index of the material. In the present case, they are selected to have substantially the same refractive index as polyvinylchloride so that the transparency is preqerved.
Methods of preparing the copolymers which constitute the base of the graft copolymers and the methods of preparing the graft copolymers them elves are already known. In the pre~ent case, the decisive factors which determine whether the graft copolymers can be used as modifying agents for vinylchloride polymers are the correct choice of catalyst and emulsifiers and the correct method of processing. The catalysts used must be a combination of a peroxydisulphate, preferably potassium or ammo-nium peroxydisulphate, and an alkanolamine, preferably trietha-nolamine cr diethanolamine. The porportions of the components of the catalyst are preferably 1:1 and the quantity of catalyst used is preferably from 0.3 to 0.5 % by weight, based on the quantity of reactants.
Suitable emulsifiers include salts of long chain fatty acids or of resinic acids, preferably sodium and potassium salts Le A 16 985 _ 3 _ 10~824~:;
of disproportionated abietic acid (alkylsulphates and alkyl-sulphonates ~re not suitable) or combinations thereof.
The compounds used as electrolytes for precipitation are preferably acids, in particular dilute acetic acid.
If the copolymer which forms the base of the graft co-polymer is required to be cross-linked, the preferred cross-linking monomer is divinylbenzene.
The graft copolymers may be used for modifying any vinyl chloride polymer, but they are particularly envisaged for poly-vinylchloride and copolymers of vinylchloride, in particular with vinylidenechloride, vinyl esters such as vinylacetate, acry-lic acid or methacrylic acid and esters thereof, nitriles and amides, maleic acid derivatives, vinyl ethers and olefinically unsaturated hydrocarbons such as ethylene, propylene and buty-lene.
A product can, of course, be expected to be transparent and colourless only if the refractive index of the vinylchloride polymer correspond~ at least approximately to that of the graft copolymer.
The particular method used for preparing the vinylchlo-rlde polymer is generally immaterial, but the usual emulsion, suspension or solvent-free polymerisation processes can be employed.
Le A 16~ _ 4 _ ,. , ~ ~ .
1088Z4~; `
General metho~ of procedure To test the surface characteristics, pulverulent mixtures were prel)ared from 88 parts by weight of poly-vinylclllori~e, 12 parts by weight of a graft polymer, 1.5 parts by weight of di-n-octyltindithioglycolic acid ester 1.0 part by weight of isotridecylstearate and 0.2 part by weight of montanic acid ester and the mixtures were blow-moulded in a single path extruder to produce tubular films.
The surface quality ol the Iilms was assessed visually.
To test the notched impact strength (DIN 53 453) transparency (expresse~ in terms of the proportion of scattered light by the ASTM Test Method D307) and white fracture (visual assessment), mixtures of 85 parts by weight of polyvinylchloride, 15 parts by weight of a graft polymer, 1.5 parts by weight of di-n-octyltindithioglycolic acid ester and 0.2 part by weight of montanic acid ester were homogenised on rollers at 180C and pressed to form plate~. The polyvinylchloride used was a product with K-value 57 produced by solvent-free polymerisation.
PreParation-of the ~xaft pol~ers Graft base 1 or 2 was introduced in the form of an approximately 50% latex into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and dropping funnels, and sufficient salt-free water was added to ~ ovide a total of 200 parts by weight. 0.01 part by weight of the disodium salt of ethylenediaminotetracetic acid was then introduced, the oxygen was replaced by nitrogen and the reac-tion mixture was heated to 65C~ 0.3 part by weight of potassium 3 peroxydisulphate in 13 parts by weight of water was then Le A 16 985 - 5 _ .
1088Z4~i addcd, lollowcd, in the course of 4 hours, by the monomer mixture, emulsifier, sodium hydroxide solution and triethanolamine. The mixture was then stirred for a further 1~ hours at ~5C and the resulting latex was stabilised with 0.5 part by weight of2,6-di-tertiary butyl-~-cresol dispersed in water.
Graft base l is a copolymer of 73% by weight of butadiene, 25~ by weight of styrene and 2~ by weight of divinylbenzene. It is provided in the form of 45.9~ latex.
The particles have an average diameter (d50) of 0.12 ~m.
Graft base 2 is a copolymer of 70~ by weight of butadiene, 20% by weight of styrene and lO~ by weight of acrylonitrile. Average particle diameter 0.08 pm. The graft base is provided as a 40.2~ latex.
Quantitative proportions and other details concerning the preparation of seven graft polymer latices are summarised in Table l. Lati~es l and 2 are in accordance with the present invention while latices 3 to 7 are com-parison products. Latices l and 2 can easily be precip-itated with 2% acetic acid and then filtered, washed and dried under vacuum Latioes 3 to 7 cannot be worked up in this way and require salt solutions for precipitation, Table 2 shows the properties of mixtures of polyvinyl-chloride and products l to 7. The mixtures were prepared and tested by the methods indicated above.
Table 3 which gives a summary of experiments 8 to lO, shows that precipitation of graft polymer latices with dilute acetic acid is posæible only if the latices contain dialkanolamine as catalyst in addition to peroxydiæulphate.
Precipitation is not possible if other amineæ are uæed.
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h E3 P ~ o O t' o ~ t~ ~ , h OD ~n p, O S~ h a~
o ~: - ~1 o ~ 1 o ~-1 h h ~ ~ ~
O ~d O
# ~ $~
~ # q~ ~
rl O ~ rl h 11 11 O C~ H V C~ +
p~ ~ ~ ~_Z; ~ ~ P~ *
Le A 16 98~ -- 8 --1088Z4~i Table 3 : Influence of varlous types of amines Parts by wei~ht Experim nt Experiment Experiment Salt-free water 200.0 200.0 200.0 Graft base 1 50.0 50.0 50.0 Styrene 25.0 25.025,0 , Methylmethacrylate22.5 22.5 22.5 Acrylonitrile 2,5 2.5 2.5 Na salt of disproportion-ated abietic acid 1.5 1.5 1.5 N sodium hydroxide solution 1.25 1.25 1.25 Disodium salt of ethylenediaminotetracetic acid 0.01 0.01 0.01 Potassium peroxydisulphate 0.3 0.3 0.3 Tributylamine 0.37 . - _ Diethylolamine - 0.21 iethylaminoethanol - - 0.24 Precipitation with :: acetic acid l.-Q.~.2~ _ 9 _ .
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of modifying a vinylchloride polymer wherein from 98 to 80%
by weight of the vinylchloride polymer is mixed with from 2 to 20% by weight of a rubbery-elastic graft copolymer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 µm, the graft copolymer having been prepared by emulsion polymerisation of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsi-fier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
by weight of the vinylchloride polymer is mixed with from 2 to 20% by weight of a rubbery-elastic graft copolymer of (A) 40 to 70 parts by weight of a monomer mixture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of butadiene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acrylonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 µm, the graft copolymer having been prepared by emulsion polymerisation of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a catalyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsi-fier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH value below 7.
2. A method as claimed in Claim 1, wherein the vinylchloride polymer is the homopolymer polyvinylchloride.
3. A method as claimed in Claim 1, wherein the vinylchloride polymer is a copolymer of vinylchloride with vinylidenechloride, a vinyl ester, acrylic or methacrylic acid or esters thereof, a nitrile, an amide, a maleic acid derivative, a vinyl ether or an olefinically unsaturated hydrocarbon.
4. A modified vinylchloride polymer which comprises from 98 to 80% by weight of vinylchloride polymer mixed with from 2 to 20% by weight of a rub bery-elastic graft copolymer of (A) 40 to 70 parts by weight of a monomer mix-ture of 40 to 60 parts by weight of styrene, 40 to 60 parts by weight of methylmethacrylate and 0 to 10 parts by weight of acrylonitrile on (B) from 60 to 30 parts by weight of a copolymer of 70 to 90 parts by weight of buta-diene, 10 to 30 parts by weight of styrene, 0 to 10 parts by weight of acry-lonitrile and 0 to 2 parts by weight of a cross-linking monomer having an average particle size of from 0.05 to 0.5 µm, the graft copolymer having been prepared by emulsion polymerisation of a mixture of the monomers of (A) in the presence of the copolymer (B) in the form of a latex with the aid of a cata-lyst system consisting of a peroxydisulphate and an alkanolamine and of an emulsifier which is active at a pH value above 7, followed by isolation of the graft copolymer from the latex by precipitation with an electrolyte at a pH
value below 7.
value below 7.
5. A modified vinylchloride polymer as claimed in Claim 4, wherein the vinylchloride polymer is the homopolymer polyvinylchloride.
6. A modified vinylchloride polymer as claimed in Claim 4, wherein the vinylchloride polymer is a copolymer of vinylchloride with vinylidenechloride a vinyl ester, acrylic or methacrylic acid or esters thereof, a nitrile, an amide, a maleic acid derivative, a vinyl ether or an olefinically unsaturated hydrocarbon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2603992A DE2603992A1 (en) | 1976-02-03 | 1976-02-03 | MODIFICATION OF VINYL CHLORIDE POLYMERIZES |
| DEP2603992.9 | 1976-02-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1088246A true CA1088246A (en) | 1980-10-21 |
Family
ID=5968893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,832A Expired CA1088246A (en) | 1976-02-03 | 1977-02-01 | Modification of vinylchloride polymers |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5295760A (en) |
| AU (1) | AU502479B2 (en) |
| BE (1) | BE851041A (en) |
| BR (1) | BR7700616A (en) |
| CA (1) | CA1088246A (en) |
| DE (1) | DE2603992A1 (en) |
| ES (1) | ES455416A1 (en) |
| FR (1) | FR2340345A1 (en) |
| GB (1) | GB1541193A (en) |
| IT (1) | IT1083468B (en) |
| NL (1) | NL7701043A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60108454A (en) * | 1983-11-18 | 1985-06-13 | Japan Synthetic Rubber Co Ltd | Vinyl chloride resin composition |
| JP2896378B2 (en) * | 1989-03-23 | 1999-05-31 | ジェイエスアール株式会社 | Rubber modified styrenic resin composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL300635A (en) * | 1962-11-19 | |||
| DE1470866B2 (en) * | 1962-12-24 | 1971-01-21 | Kanegafuchi Chemical Industry Co, Ltd, Osaka (Japan) | Thermoplastic molding compounds |
| GB1086888A (en) * | 1965-01-25 | 1967-10-11 | Kanegafuchi Chemical Ind | Vinyl chloride-butadiene resin compositions and method of manufacture |
| US3670052A (en) * | 1965-01-25 | 1972-06-13 | Kanegafuchi Chemical Ind | Thermoplastic vinyl resin compositions, and method of manufacture |
| BE719425A (en) * | 1967-08-19 | 1969-01-16 | ||
| FR2161909B1 (en) * | 1971-10-07 | 1975-06-13 | Kureha Chemical Ind Co Ltd | |
| JPS5337908B2 (en) * | 1973-07-26 | 1978-10-12 |
-
1976
- 1976-02-03 DE DE2603992A patent/DE2603992A1/en not_active Withdrawn
-
1977
- 1977-01-01 BR BR7700616A patent/BR7700616A/en unknown
- 1977-01-27 AU AU21717/77A patent/AU502479B2/en not_active Expired
- 1977-01-28 ES ES455416A patent/ES455416A1/en not_active Expired
- 1977-01-31 GB GB3828/77A patent/GB1541193A/en not_active Expired
- 1977-02-01 JP JP932477A patent/JPS5295760A/en active Pending
- 1977-02-01 CA CA270,832A patent/CA1088246A/en not_active Expired
- 1977-02-01 IT IT47864/77A patent/IT1083468B/en active
- 1977-02-01 NL NL7701043A patent/NL7701043A/en not_active Application Discontinuation
- 1977-02-03 FR FR7703063A patent/FR2340345A1/en active Granted
- 1977-02-03 BE BE174619A patent/BE851041A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2603992A1 (en) | 1977-08-04 |
| AU2171777A (en) | 1978-08-03 |
| BR7700616A (en) | 1977-10-04 |
| IT1083468B (en) | 1985-05-21 |
| GB1541193A (en) | 1979-02-21 |
| AU502479B2 (en) | 1979-07-26 |
| JPS5295760A (en) | 1977-08-11 |
| FR2340345A1 (en) | 1977-09-02 |
| NL7701043A (en) | 1977-08-05 |
| FR2340345B1 (en) | 1983-08-19 |
| BE851041A (en) | 1977-08-03 |
| ES455416A1 (en) | 1978-01-01 |
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