CA1160798A - Process for the manufacture of a vinyl ester copolymer - Google Patents
Process for the manufacture of a vinyl ester copolymerInfo
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- CA1160798A CA1160798A CA000315843A CA315843A CA1160798A CA 1160798 A CA1160798 A CA 1160798A CA 000315843 A CA000315843 A CA 000315843A CA 315843 A CA315843 A CA 315843A CA 1160798 A CA1160798 A CA 1160798A
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- vinyl ester
- crotonic acid
- polymerization
- vinyl
- weight
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Abstract
Abstract Of the disclosure:
Copolymers of vinyl esters and crotonic acid are com-monly prepared by polymerizing the monomers in bulk or in solution by means of a radical-forming initiator in the presence of a regulator. The polymers should be free from residual monomers and impurities as far as possible.
This may be realized in that upon completion of the poly-merization the unreacted monomers and other volatile impu-rities are removed from the are removed from the reaction mixture by distilluation For this purpose, the use of an entrainer is advantageous.
The copolymers are suitable as starting materials for adhesives and hair lacquers, hair setting lotions as well as hair sprays.
Copolymers of vinyl esters and crotonic acid are com-monly prepared by polymerizing the monomers in bulk or in solution by means of a radical-forming initiator in the presence of a regulator. The polymers should be free from residual monomers and impurities as far as possible.
This may be realized in that upon completion of the poly-merization the unreacted monomers and other volatile impu-rities are removed from the are removed from the reaction mixture by distilluation For this purpose, the use of an entrainer is advantageous.
The copolymers are suitable as starting materials for adhesives and hair lacquers, hair setting lotions as well as hair sprays.
Description
The present invention relates to a process for the manu-facture of a vinyl ester copolymer.
The manufacture of copolymers of vinyl ester and crotonic acid is effected by polymerizing the monomers in bulk or in solution in the presence of a radical-forming initiator and usually in the presence of a regulator which is to adjust the molecular weight and the polymerization rate. The known copolymers are suitable in the form of alcoho~ic solutions as film-forming agents or binders in hair sprays and hair setting lotions.
The known copolymers very frequently show the drawback that they still contain a remainder of unreacted monomers and impur-ities; this leads to an unpleasant smell and may cause skin irrita-tion when using these substances. It is therefore the object of the invention to manufacture vinyl ester/crotonic acid copolymers with little smell, which do not exhibit the drawbacks of the known copolymers.
~ he invention provides a process for the manufacture of a copolymer of at least one vinyl ester and crotonic acid which com-prises copolymerizing 70% to 90% by weight of the total amount of vinyl ester with the total amount of crotonic acid in the presence of a radical-forming initiator and a polymerization regulator, add-ing the remainder of the vinyl ester to the polymerization reaction mixture and completing the polymerization, mixing the polymer with an entrainer which is an alkanol of 1 to 4 carbon atoms that may contain up to 20% by weight of water and heating the resulting mix-ture to vaporize at least a part of said alkanol and thereby distill from said copolymer residual monomer and other volatile impurities.
The polymerization is optionally carried out in the presence of a polyalkylene glycol.
The manufacture of copolymers of vinyl ester and crotonic acid is effected by polymerizing the monomers in bulk or in solution in the presence of a radical-forming initiator and usually in the presence of a regulator which is to adjust the molecular weight and the polymerization rate. The known copolymers are suitable in the form of alcoho~ic solutions as film-forming agents or binders in hair sprays and hair setting lotions.
The known copolymers very frequently show the drawback that they still contain a remainder of unreacted monomers and impur-ities; this leads to an unpleasant smell and may cause skin irrita-tion when using these substances. It is therefore the object of the invention to manufacture vinyl ester/crotonic acid copolymers with little smell, which do not exhibit the drawbacks of the known copolymers.
~ he invention provides a process for the manufacture of a copolymer of at least one vinyl ester and crotonic acid which com-prises copolymerizing 70% to 90% by weight of the total amount of vinyl ester with the total amount of crotonic acid in the presence of a radical-forming initiator and a polymerization regulator, add-ing the remainder of the vinyl ester to the polymerization reaction mixture and completing the polymerization, mixing the polymer with an entrainer which is an alkanol of 1 to 4 carbon atoms that may contain up to 20% by weight of water and heating the resulting mix-ture to vaporize at least a part of said alkanol and thereby distill from said copolymer residual monomer and other volatile impurities.
The polymerization is optionally carried out in the presence of a polyalkylene glycol.
- 2 -Within the framework of the invention there are used as vinyl esters above all vinyl esters of lower aliphatic monocarboxylic acids, especially com~
pounds of the formula CH = CH - 0 - C0 - R
in which R is an alkyl radical of fram i, 2 or 3 carbon atcms, for example vinyl aoe tate, vinyl propionate and vinyl butyrate. Preference is given in particular to vinyl acetate. Instead of a single vinyl ester there may also be used a mix-ture of several different vinyl esters.
As radical-forming initiators there are used peroxy oompounds and aliphatic azo oompounds, for example diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisopropyl percarbonate, tertiary butyl peroctoate, di-tertiary butyl pe mxide and cumene hydroperoxide as well as azodiisobutyric acid nitrile and azo dicarbonamide. The amount of the initiator is in the range of fmm 0.01 to 5, preferably from 0.1 to 2 % by weight, calculated on the total amount of the oompounds to be polymerized.
The polymerization is ocmmanly carried out in a tem~erature range of from 25& below the boiling temperature of the reaction mixture to the boiling temperature of the same. The temperature range of from 50 to 120&, preferably from 70 to lOo&, is recornendel. It is advantageous to carry out the polymeriza-tion under an inert gas atmosphere. As inert gases there may be used above allnitrogen and ncble gases, such as argon.
As regulators there may be mentioned aliphatic mercaptans, lower aliphatic aldehydes and lower alkanols, especially aliphatic mercaptans having from 4 to 16 c æbon l 16079~
- 4 - HOE 77/F 2?8 atoms, for example n-butyl mercaptan, t-butyl mercaptan and n-dodecyl mercaptan, furthermore, aliphatic aldehydes of from 2 to 4 carbon atoms, for example acetaldehyde, pro pionaldehyde and butyraldehyde, as well as alkanols of from 1 to 4 carbon atoms, for example methanol, ethanol, isopro-panol and t-butanol.
A preferred embodiment of the process of the invention is the execution of the polymerization in two stages, according to which the main amount of the vinyl ester is at first polymerized with the total amount of the crotonic acid and optionally the total amount of the polyalkylene glycol, and thereafter the polymerization is oompleted after adding the remainder of vinyl ester. The weight ratio of the monomers vinyl ester/crotonic acid that are used altogether is in the range of from 100 : 1 to 100 :
20, preferably from 100 : 5 to 100 : 15. In the first polymerization stage~ from 70 to 98 % by weight of the total amount of the vinyl ester are normally used, prefe-rably from 80 to 95 % by weight; in this process the crotonic acid employed is polymerized almost completely.
The polymerization of the remaining 2 to 30, preferably from 5 to 20 g by weight of the total amount of the vinyl e~ter is then effected in the second stage, optionally while adding an additional amount of initiator.
Arl essential feature of the process of the invention is to be seen in the measure that upon completion of the polymerization the remaining unreacted monomers and possible volatile impurities, which have been introduced with the 29 monomers into the reaction mixture or have been formed in ... ..
l 160798 - 5 - H0~ 77/F 228 the course of the reaction, are removed from the reaction mixture by way of distillation, so that the vinyl ester copolymer extracted is obtained in a largely pure form and with little smell. ~or this purpose it is advantageous to use an entrainer in which the copolymer is at least partial-ly soluble or swellable. As entrainers there are suitable ~B~ in particular lower alkanols of from 1 to ~ carbon atoms, for example methanol, ethanol a~d isopropanol; the entrai-ner may contain up to 20 % by weight of water. Said entrai-ner is employed in an amount of from 5 to 50, preferably 10to 30 ~ by weight, calculated on the copolymer. It is advantageous to mix the entrainer with the copolymer which upon completion of the polymerization is present in a melted form, however, it may also be added to the reaction mixture before or during the polymerization, if it does not disturb the reaction. The entrainer which is removed by di~tillation may be used several times without working-up.
If a vinyl ester and crotonic acid are used as the only polymerizable compounds, the process of the invention leads to copolymers with a statistical distribution of the monomer units However, if a polyalkylene glycol is addi-tionally employed, graft copolymers are obtained.
As polyalkylene g~ycols there are suitable above all polyalkylene glycols with an average molecular weight (numerical average) of from 106 to 25,000, preferably from 1,000 to 15,000, i.e. oligomer compounds and higher molecu-lar weight polymers of aliphatic diols or corresponding cyc-lic ethers. As oligomers there may be mentioned diethylene glycol, triethylene glycol, tetraethylene glycol as well as dipropylene glycol and tripropylene glycol; as polyrners --` I 160798 ! . - 6 - HOE 77/F 228 there are mentioned especially polyethylene glycol and polypropylene glycol. Copolymers of different cyclic ether~, especially of ethylene oxide and 1,2-propylene oxide, may also be used.
The po].ymers obtained according to the invention are suitabl~ as starting materials for adhesives and especially for hair lacquers, hair setting lotions and hair sprays.
In the field ol cosmetics they are commonly used in the form of diluted solutions in mixtures of water and lower a].cohols, especially ethanol or isopropanol. The polymer content of solutions of this kind is generally in the range of from 2 to 5 % by weight.
The following Examples illustrate the invention and show the advantages over the state of the art, which may be seen from the compariqon examples. All percentages relate to the weight; ~'ppm" means "parts per million~. The mono-mer content of the polymer solution i8 determined in each oa3~ by way of gas chromatography.
E X A M P L E 1: .
15 Per cent of a mixture of 56 kg of vinyl acetate, 6.3 kg of crotonic acid, 1.3 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into a stirring vessel having a cap~city of 100 liters and being flushed with nitrogen, the vessel being provided with a reflux condenser, a jacket heating and cooling, and said mixture is heated to reflux temperture (about 70C). In the course of 7 hours the remaining 85 ~ of the above mixture are uniformly added, in which process the polymerization heat is carried off by 29 the jacket cooling in a manner that a slight reflux is .
l 160798 maintained and the internal temperature rises slowly to 90 to 95C. Subsequently 7 kg of vinyl acetate are added in doses in the course of 1 hour.
After having been heated for 2 hours at 95C, the reaction mixture is distilled under reduced pressure (about 70 mbars) for 5 hours. The remaining polymer melt is let off into a trough and is allowed to cool therein the room temperature and solidifies. From the polymer thus obtained, a 60 % solution in ethanol is prepared; it contains 65 ppm of crotonic acid and 1,210 ppm of vinyl acetate. This solution is concentrated to a solids content of 70 % by removing ethanol by distillation, thereafter it is diluted again with ethanol to a content of 60 %; it now contains 60 ppm of crotonic acid and 340 ppm of vinyl acetate and is almost odorless.
E X A M P L E 2:
.. ... . _ The process is carried out as has been described in Example l, however, the starting mixture is composed of 49 kg of vinyl acetate, 6.3 kg of crotonic acid, l.l kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde, and the introduction of the 85 ~ portion takes 6 hours; in the second stage, 14 kg of vinyl acetate, in which 0.24 kg of dibenzoyl peroxide is dissolved, are added in doses in the course of 2 hours.
The 60 % solution in ethanol prepared from the polymer obtained is concentrated to a solids content of 80 % by distilling off ethanol, and thereafter said mixture is again diluted with ethanol to a content of 60 ~. The 29 solution then contains 27 ppm of crotonic acid and 65 ppm l 160798 of vinyl acetate and is odorless.
E X A M P L E 3:
The process is carried out as has been described in Example 1, however, the starting mixture consists of 42 kg of vinyl acetate, 6.3 kg of crotonic acid, 1 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde, and the introduction of the 85 % portion takes 5 hours; in the second stage, 21 kg of vinyl acetate, in which 0.34 kg of dibenzoyl peroxide is dissolved, are added in doses within 3 hours.
The 60 % solution in ethanol prepared from the polymer obtained contains 11 ppm of crotonic acid and 1.215 ppm of vinyl acetate. It is concentrated to a solids content of 90 ~ by distilling off ethanol, and subsequently it is diluted again to a content of 60 % with ethanol. This solution contains now less than 10 ppm of crotonic acid and less than 20 ppm of vinyl acetate and is odorless.
OMPARISON EXAMPLE 1.
15 Per ¢ent of a mixture of 63 kg of vinyl acetate, 6.3 kg of crotonic acid, 1.3 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into the vessel describ-ed in Example 1 and the mixture is heated to reflux tempe-ratùre (about 70C). In the course of 8 hours the remain-ing 85 % of the above-mentioned mixture are uniformly added, the rise in temperature being regulated according to Example 1.
After having been heated for another 2 hours at 9:jC, the reaction mixture is distilled under reduced pres~ure (about 70 mbars) for 5 hours. The remaining polymer melt 29 is let off into a trough, where it is allowed to cool to room temperature and solidi~ies. From the polymer obtained, a 60 % solution in ethanol is prepared; the solution having a strong smell contains 186 ppm of crotonic acid and 1.260 ppm of vinyl acetate.
E X A M P L E 4:
6 Kilograms of polyethylene glycol having an average molecular weight of 4,000 and 15 % of a mixture of 48 kg of . vinyl acetate, 4.8 kg of crotonic acid, 1.2 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into the vessel described in Example 1, and the mixture is heated to reflux temperature (about 70C). In the course of 6 hours the remaining 85 % of the above-mentioned mixture are uniformly added, the rise in temperature being regulat-ed according to Example 1. Subsequently 12 kg of vinyl acetate, in which 0.3 kg of dibenzoyl peroxide is dissolved, are added in doses in the second stage within 2 hours.
After having been heated for another 2 hours at 95C, the reaction mixture is distilled for 5 hours under reduced pressure (about 70 mbars). The remaining polymer melt is ~et off into a trough and is allowed to cool therein to room temperature and solidifies. From the polymer obtained a 60 % solution is prepared in an isopropanol/water mixture (87~13), which contains 35 ppm of crotonic acid and 1,350 ppm of vinyl acetate. This solution is concentrated to a solids content of 80 % by distilling off the solvent and is then diluted a~ain to a content of 60 % with the sarne solvent; it then contains 33 ppm of crotonic acid ..nd 60 ppm of vinyl acetate and is almost free from any smell.
. . .
.
`~ l 160798 E X A M P L E 5:
The process is ^arried out as has been described in Example 4, however, while introducing 6 kg of polypropylene glycol having an average molecular weight of 2,000 and 4 kg of isopropanol, and the starting mixture consists of 48 kg of vinyl acetate, 4,8 kg of crotonic acid and 1.2 kg of tertiary butyl peroctoate; the introduction of the 85 %
portion takes 6 hours. In the second stage, 12 kg of vinyl acetate, in which 0.3 kg of tertiary butyl peroctoate has been dissolved, are added in doses in the course of 2 hours.
The 60 % solution in isopropanol/water (87/13) prepar-ed from a sample of the polymer obtained contains 32 ppm of crotonic acid and 970 ppm o~ vinyl acetate. Thereafter 600 g of the solid polymer are melted together with 600 g of i~opropanol. Subse~uently 252 g of isopropanol are distill-ed off, and 52 ml of water are added, while stirring. The 60 % solutlon thus obtained contains 30 ppm of crotonic acid and 55 ppm of vinyl acetate.
6 Kilograms of polyethylene glycol having an average molecular weight of 4,000 and 15 % of a mixture of 60 kg of vinyl acetate, 4.8 kg of crotonic acid, 1.5 kg of dibenzoyl peroxide and 0.25 kg Or acetaldehyde are placed into the vessel described in Example 1, and the mixture is heated to reflux temperature (about 70C). In the course of 8 hours, the remaining 85 ~ of the above-mentioned mixture are uni-formly added, the rise in temperature being regulated in accordance with Example 1.
29 After having been heated for another 2 hours at 95C, l 160798 the reaction mixture is distilled for 5 hours under reduced pressure (about 70 mbars). The remaining polymer melt is let off into a trough, where it is allowed to cool to room temperature and solidifies. Erom the polymer thus obtained, a 60 % solution in an isopropanol/water mixture (87/13) is prepared, which solution contains 197 ppm of crotonic acid and 1.320 ppm of vinyl acetate.
The process is carried out as has been described in Comparison Example 2, however, while using instead of poly-ethylene glycol polypropylene glycol having an average molecular weight of 2,000, and as starting mixture there is used a mixture of 60 kg of vinyl acetate, 4.8 kg of crotonic acid and 1.5 kg of tertiary butyl peroctoate.
The 60 % solution in isopropanol/water (87/13) prepar-ed from the polymer obtained contains 210 ppm of crotonic acid and 1,130 ppm of vinyl acetate.
pounds of the formula CH = CH - 0 - C0 - R
in which R is an alkyl radical of fram i, 2 or 3 carbon atcms, for example vinyl aoe tate, vinyl propionate and vinyl butyrate. Preference is given in particular to vinyl acetate. Instead of a single vinyl ester there may also be used a mix-ture of several different vinyl esters.
As radical-forming initiators there are used peroxy oompounds and aliphatic azo oompounds, for example diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisopropyl percarbonate, tertiary butyl peroctoate, di-tertiary butyl pe mxide and cumene hydroperoxide as well as azodiisobutyric acid nitrile and azo dicarbonamide. The amount of the initiator is in the range of fmm 0.01 to 5, preferably from 0.1 to 2 % by weight, calculated on the total amount of the oompounds to be polymerized.
The polymerization is ocmmanly carried out in a tem~erature range of from 25& below the boiling temperature of the reaction mixture to the boiling temperature of the same. The temperature range of from 50 to 120&, preferably from 70 to lOo&, is recornendel. It is advantageous to carry out the polymeriza-tion under an inert gas atmosphere. As inert gases there may be used above allnitrogen and ncble gases, such as argon.
As regulators there may be mentioned aliphatic mercaptans, lower aliphatic aldehydes and lower alkanols, especially aliphatic mercaptans having from 4 to 16 c æbon l 16079~
- 4 - HOE 77/F 2?8 atoms, for example n-butyl mercaptan, t-butyl mercaptan and n-dodecyl mercaptan, furthermore, aliphatic aldehydes of from 2 to 4 carbon atoms, for example acetaldehyde, pro pionaldehyde and butyraldehyde, as well as alkanols of from 1 to 4 carbon atoms, for example methanol, ethanol, isopro-panol and t-butanol.
A preferred embodiment of the process of the invention is the execution of the polymerization in two stages, according to which the main amount of the vinyl ester is at first polymerized with the total amount of the crotonic acid and optionally the total amount of the polyalkylene glycol, and thereafter the polymerization is oompleted after adding the remainder of vinyl ester. The weight ratio of the monomers vinyl ester/crotonic acid that are used altogether is in the range of from 100 : 1 to 100 :
20, preferably from 100 : 5 to 100 : 15. In the first polymerization stage~ from 70 to 98 % by weight of the total amount of the vinyl ester are normally used, prefe-rably from 80 to 95 % by weight; in this process the crotonic acid employed is polymerized almost completely.
The polymerization of the remaining 2 to 30, preferably from 5 to 20 g by weight of the total amount of the vinyl e~ter is then effected in the second stage, optionally while adding an additional amount of initiator.
Arl essential feature of the process of the invention is to be seen in the measure that upon completion of the polymerization the remaining unreacted monomers and possible volatile impurities, which have been introduced with the 29 monomers into the reaction mixture or have been formed in ... ..
l 160798 - 5 - H0~ 77/F 228 the course of the reaction, are removed from the reaction mixture by way of distillation, so that the vinyl ester copolymer extracted is obtained in a largely pure form and with little smell. ~or this purpose it is advantageous to use an entrainer in which the copolymer is at least partial-ly soluble or swellable. As entrainers there are suitable ~B~ in particular lower alkanols of from 1 to ~ carbon atoms, for example methanol, ethanol a~d isopropanol; the entrai-ner may contain up to 20 % by weight of water. Said entrai-ner is employed in an amount of from 5 to 50, preferably 10to 30 ~ by weight, calculated on the copolymer. It is advantageous to mix the entrainer with the copolymer which upon completion of the polymerization is present in a melted form, however, it may also be added to the reaction mixture before or during the polymerization, if it does not disturb the reaction. The entrainer which is removed by di~tillation may be used several times without working-up.
If a vinyl ester and crotonic acid are used as the only polymerizable compounds, the process of the invention leads to copolymers with a statistical distribution of the monomer units However, if a polyalkylene glycol is addi-tionally employed, graft copolymers are obtained.
As polyalkylene g~ycols there are suitable above all polyalkylene glycols with an average molecular weight (numerical average) of from 106 to 25,000, preferably from 1,000 to 15,000, i.e. oligomer compounds and higher molecu-lar weight polymers of aliphatic diols or corresponding cyc-lic ethers. As oligomers there may be mentioned diethylene glycol, triethylene glycol, tetraethylene glycol as well as dipropylene glycol and tripropylene glycol; as polyrners --` I 160798 ! . - 6 - HOE 77/F 228 there are mentioned especially polyethylene glycol and polypropylene glycol. Copolymers of different cyclic ether~, especially of ethylene oxide and 1,2-propylene oxide, may also be used.
The po].ymers obtained according to the invention are suitabl~ as starting materials for adhesives and especially for hair lacquers, hair setting lotions and hair sprays.
In the field ol cosmetics they are commonly used in the form of diluted solutions in mixtures of water and lower a].cohols, especially ethanol or isopropanol. The polymer content of solutions of this kind is generally in the range of from 2 to 5 % by weight.
The following Examples illustrate the invention and show the advantages over the state of the art, which may be seen from the compariqon examples. All percentages relate to the weight; ~'ppm" means "parts per million~. The mono-mer content of the polymer solution i8 determined in each oa3~ by way of gas chromatography.
E X A M P L E 1: .
15 Per cent of a mixture of 56 kg of vinyl acetate, 6.3 kg of crotonic acid, 1.3 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into a stirring vessel having a cap~city of 100 liters and being flushed with nitrogen, the vessel being provided with a reflux condenser, a jacket heating and cooling, and said mixture is heated to reflux temperture (about 70C). In the course of 7 hours the remaining 85 ~ of the above mixture are uniformly added, in which process the polymerization heat is carried off by 29 the jacket cooling in a manner that a slight reflux is .
l 160798 maintained and the internal temperature rises slowly to 90 to 95C. Subsequently 7 kg of vinyl acetate are added in doses in the course of 1 hour.
After having been heated for 2 hours at 95C, the reaction mixture is distilled under reduced pressure (about 70 mbars) for 5 hours. The remaining polymer melt is let off into a trough and is allowed to cool therein the room temperature and solidifies. From the polymer thus obtained, a 60 % solution in ethanol is prepared; it contains 65 ppm of crotonic acid and 1,210 ppm of vinyl acetate. This solution is concentrated to a solids content of 70 % by removing ethanol by distillation, thereafter it is diluted again with ethanol to a content of 60 %; it now contains 60 ppm of crotonic acid and 340 ppm of vinyl acetate and is almost odorless.
E X A M P L E 2:
.. ... . _ The process is carried out as has been described in Example l, however, the starting mixture is composed of 49 kg of vinyl acetate, 6.3 kg of crotonic acid, l.l kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde, and the introduction of the 85 ~ portion takes 6 hours; in the second stage, 14 kg of vinyl acetate, in which 0.24 kg of dibenzoyl peroxide is dissolved, are added in doses in the course of 2 hours.
The 60 % solution in ethanol prepared from the polymer obtained is concentrated to a solids content of 80 % by distilling off ethanol, and thereafter said mixture is again diluted with ethanol to a content of 60 ~. The 29 solution then contains 27 ppm of crotonic acid and 65 ppm l 160798 of vinyl acetate and is odorless.
E X A M P L E 3:
The process is carried out as has been described in Example 1, however, the starting mixture consists of 42 kg of vinyl acetate, 6.3 kg of crotonic acid, 1 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde, and the introduction of the 85 % portion takes 5 hours; in the second stage, 21 kg of vinyl acetate, in which 0.34 kg of dibenzoyl peroxide is dissolved, are added in doses within 3 hours.
The 60 % solution in ethanol prepared from the polymer obtained contains 11 ppm of crotonic acid and 1.215 ppm of vinyl acetate. It is concentrated to a solids content of 90 ~ by distilling off ethanol, and subsequently it is diluted again to a content of 60 % with ethanol. This solution contains now less than 10 ppm of crotonic acid and less than 20 ppm of vinyl acetate and is odorless.
OMPARISON EXAMPLE 1.
15 Per ¢ent of a mixture of 63 kg of vinyl acetate, 6.3 kg of crotonic acid, 1.3 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into the vessel describ-ed in Example 1 and the mixture is heated to reflux tempe-ratùre (about 70C). In the course of 8 hours the remain-ing 85 % of the above-mentioned mixture are uniformly added, the rise in temperature being regulated according to Example 1.
After having been heated for another 2 hours at 9:jC, the reaction mixture is distilled under reduced pres~ure (about 70 mbars) for 5 hours. The remaining polymer melt 29 is let off into a trough, where it is allowed to cool to room temperature and solidi~ies. From the polymer obtained, a 60 % solution in ethanol is prepared; the solution having a strong smell contains 186 ppm of crotonic acid and 1.260 ppm of vinyl acetate.
E X A M P L E 4:
6 Kilograms of polyethylene glycol having an average molecular weight of 4,000 and 15 % of a mixture of 48 kg of . vinyl acetate, 4.8 kg of crotonic acid, 1.2 kg of dibenzoyl peroxide and 0.25 kg of acetaldehyde are placed into the vessel described in Example 1, and the mixture is heated to reflux temperature (about 70C). In the course of 6 hours the remaining 85 % of the above-mentioned mixture are uniformly added, the rise in temperature being regulat-ed according to Example 1. Subsequently 12 kg of vinyl acetate, in which 0.3 kg of dibenzoyl peroxide is dissolved, are added in doses in the second stage within 2 hours.
After having been heated for another 2 hours at 95C, the reaction mixture is distilled for 5 hours under reduced pressure (about 70 mbars). The remaining polymer melt is ~et off into a trough and is allowed to cool therein to room temperature and solidifies. From the polymer obtained a 60 % solution is prepared in an isopropanol/water mixture (87~13), which contains 35 ppm of crotonic acid and 1,350 ppm of vinyl acetate. This solution is concentrated to a solids content of 80 % by distilling off the solvent and is then diluted a~ain to a content of 60 % with the sarne solvent; it then contains 33 ppm of crotonic acid ..nd 60 ppm of vinyl acetate and is almost free from any smell.
. . .
.
`~ l 160798 E X A M P L E 5:
The process is ^arried out as has been described in Example 4, however, while introducing 6 kg of polypropylene glycol having an average molecular weight of 2,000 and 4 kg of isopropanol, and the starting mixture consists of 48 kg of vinyl acetate, 4,8 kg of crotonic acid and 1.2 kg of tertiary butyl peroctoate; the introduction of the 85 %
portion takes 6 hours. In the second stage, 12 kg of vinyl acetate, in which 0.3 kg of tertiary butyl peroctoate has been dissolved, are added in doses in the course of 2 hours.
The 60 % solution in isopropanol/water (87/13) prepar-ed from a sample of the polymer obtained contains 32 ppm of crotonic acid and 970 ppm o~ vinyl acetate. Thereafter 600 g of the solid polymer are melted together with 600 g of i~opropanol. Subse~uently 252 g of isopropanol are distill-ed off, and 52 ml of water are added, while stirring. The 60 % solutlon thus obtained contains 30 ppm of crotonic acid and 55 ppm of vinyl acetate.
6 Kilograms of polyethylene glycol having an average molecular weight of 4,000 and 15 % of a mixture of 60 kg of vinyl acetate, 4.8 kg of crotonic acid, 1.5 kg of dibenzoyl peroxide and 0.25 kg Or acetaldehyde are placed into the vessel described in Example 1, and the mixture is heated to reflux temperature (about 70C). In the course of 8 hours, the remaining 85 ~ of the above-mentioned mixture are uni-formly added, the rise in temperature being regulated in accordance with Example 1.
29 After having been heated for another 2 hours at 95C, l 160798 the reaction mixture is distilled for 5 hours under reduced pressure (about 70 mbars). The remaining polymer melt is let off into a trough, where it is allowed to cool to room temperature and solidifies. Erom the polymer thus obtained, a 60 % solution in an isopropanol/water mixture (87/13) is prepared, which solution contains 197 ppm of crotonic acid and 1.320 ppm of vinyl acetate.
The process is carried out as has been described in Comparison Example 2, however, while using instead of poly-ethylene glycol polypropylene glycol having an average molecular weight of 2,000, and as starting mixture there is used a mixture of 60 kg of vinyl acetate, 4.8 kg of crotonic acid and 1.5 kg of tertiary butyl peroctoate.
The 60 % solution in isopropanol/water (87/13) prepar-ed from the polymer obtained contains 210 ppm of crotonic acid and 1,130 ppm of vinyl acetate.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of a copolymer of at least one vinyl ester and crotonic acid which comprises copolymerizing 70% to 98% by weight of the total amount of vinyl ester with the total amount of crotonic acid in the presence of a radical-forming initiator and a polymerization regulator, adding the remainder of the vinyl ester to the polymerization reaction mixture and completing the polymerization, mixing the polymer with an entrainer which is an alkanol of 1 to 4 carbon atoms that may contain up to 20% by weight of water and heating the resulting mixture to vaporize at least a part of said alkanol and thereby distill from said copolymer residual monomer and other volatile impurities.
2. The process of claim 1 which comprises using a vinyl ester vinyl acetate, vinyl propionate or vinyl butyrate along or an admixture.
3. A vinyl ester/crotonic acid copolymer obtained accord-ing to the process as claimed in claim 1.
4. A process for the manufacture of a copolymer of at least one vinyl ester and crotonic acid which comprises copolymerizing the vinyl ester and crotonic acid in a two-stage polymerization using a vinyl ester/crotonic acid weight ratio 100:1 to 100:20, in the first stage copolymerizing a portion comprising 70% to 98% by weight of the total amount of the vinyl ester with the total amount of crotonic acid in the presence of a radical-forming initi-ator and a polymerization regulator, in the second stage adding the remainder of the vinyl ester to the polymerization mixture and completing the polymerization, dissolving the polymer in an entrainer which is an alkanol of 1 to 4 carbon atoms that may contain up to 20% by weight of water and heating the resulting solution to vaporize at least a part of said alkanol and thereby distill from said copolymer solution residual monomer and other volatile impurities.
5. A process according to claim 1 or 4 wherein the copolymerization is carried out in the presence of a polyalkylene glycol to form a graft polymer.
6. A process according to claim 1 or 4 wherein the copolymerization is carried out in the presence of poly(ethylene glycol) or poly(propylene glycol) or both, to form a graft polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000315843A CA1160798A (en) | 1978-11-06 | 1978-11-06 | Process for the manufacture of a vinyl ester copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000315843A CA1160798A (en) | 1978-11-06 | 1978-11-06 | Process for the manufacture of a vinyl ester copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160798A true CA1160798A (en) | 1984-01-17 |
Family
ID=4112896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000315843A Expired CA1160798A (en) | 1978-11-06 | 1978-11-06 | Process for the manufacture of a vinyl ester copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1160798A (en) |
-
1978
- 1978-11-06 CA CA000315843A patent/CA1160798A/en not_active Expired
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