US2419221A - Copolymers of 2-halogeno-allyl alcohol or 2-halogeno-allyl esters - Google Patents

Copolymers of 2-halogeno-allyl alcohol or 2-halogeno-allyl esters Download PDF

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Publication number
US2419221A
US2419221A US442453A US44245342A US2419221A US 2419221 A US2419221 A US 2419221A US 442453 A US442453 A US 442453A US 44245342 A US44245342 A US 44245342A US 2419221 A US2419221 A US 2419221A
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copolymer
allyl
halogeno
solution
water
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US442453A
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William O Kenyon
John H Van Campen
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US442453A priority Critical patent/US2419221A/en
Priority to FR940678D priority patent/FR940678A/fr
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/20Esters containing halogen

Definitions

  • This invention relates to copolymers of 2-halogeno-allyl alcohols or 2-halogeno-allyl esters.
  • esters of 2-chloro-ally1 alcohol containing but one ethylenic linkage, viz. 2-chloro-allyl chloroacetate, have beenproposed as "modifiers in the polymerization of polymerizable organic compounds also containing but one ethylenic linkage, such as vinyl compounds and vinylidene chloride.
  • 2-halogeno-allyl compounds we prefer the more readily available, more stable 2-chloro-allyl compounds.
  • 2-chloroallyl esters which we have found especially useful in practicing our invention, the following can be mentioned: 2-chloro-allyl esters of monobasic in- -tate the copolymer.
  • acrylic acids such as methacrylic acid, ethacrylic acid and a-ChlOlO- acrylic acid, esters of acrylic acids, e. g. methyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methyacrylate and methyl cz-ChlOlO- acrylate.
  • the proportion of monomeric 2-halogeno-allyl compound to polymerizable organic compound containing an ethylenic linkage conjugated with another double-bond linkage can be any desired ratio. However, we have found that in the copolymer the ratio of 2-halogeno-allyl compound to the second compound is never greater than 1:1. More than one 2-halogeno-ally1 compound can be copolymerized with one polymerizable organic compound containin an ethylenic linkage conjugated with another double-bond linkage, and more than one of the compounds containing the conjugated system can be employed with on 2-halogeno-allyl compound.
  • the monomers are mixed in the desired ratio, a polymerization catalyst, e. g. an organic peroxide,- added, and the resulting mixture allowed to polymerize, advantageously with warming.
  • a polymerization catalyst e. g. an organic peroxide
  • Any of the catalysts known to effect the polymerization of vinyl compounds can be employed.
  • the resulting resin is dissolved in a suitable solvent, and the solution poured into a nonsolvent for the resin (usually water) to precipitate the resin.
  • the precipitated resin is then washed with water (and steamed,'if necessary) and finally dried.
  • the following examples and table will serve to illustrate th copolymers and the process for preparing them.
  • EXAMPLE 1 COPOLYMER or 2-CHLORO-ALLYL ALCOHOL AND METHYL-a-METHACRYLATE
  • a solution of 5 g. of methyl a-methacrylate, 5 g. of 2-chloro-allyl alcohol and 0.05 g. of benzoyl peroxide was prepared and placed in an Erlenmeyer flask. The flask was stoppered and placed in an oven at 40 C. After four and one-half months the mixture was found to be solid and slightly yellow in color. The product was dissolved in acetone and the solution diluted to cc. with acetone.
  • the diluted solution was filtered and then poured into cold water to precipi-
  • the cream colored, fibrous precipitate was soaked for two hours, filtered and dried in the air at room temperature.
  • the yield was 5.2 g.
  • the copolymer contained chlorine equal to 8.27% by weight.
  • EXAMPLE 4 --COPOLYMER or 2-CHLORO-ALLYL CHLORIDE AND METHYL or-METHACRYLATE'
  • a solution of 50 g. of methyl methacrylate, 56 g. of 2-chloro-allyl chloride and 1.06 g. of benzoyl peroxide was prepared and heated on a steam bath. After twenty-seven and one-half hours heating, 1.06 g. of benzoyl peroxide were added to the yellow, viscous liquid. At the end of two further hours of heating, the reaction mixture was very viscous. Heating was discontinued and the reaction mixture dissolved in acetone. The acetone solution was poured into hot Water to precipitate the copolymer.
  • the copolymer was then steamed for five hours.
  • the copolymer was redissolved'in acetone and the acetone solution again poured into water to precipitate the copolymer.
  • the copolymer was soaked in ethanol and again dissolved in acetone.
  • the acetone solution was again poured into water to precipitate the copolymer.
  • the copolymer was filtered off and dried at room temperature. The slightly yellow, friable product weighed 75 g. and con tained 28% by weight of chlorine.
  • the copolymer was then redissolved in dioxane and reprecipitated by pouring the solution into water.
  • the copolymer was filtered ofi and dried in the air at room temperature.
  • the colorless, friable copolymer weighed 5.7 g. and contained 15.49% by weight of chlorine.
  • EXAMPLE 8 COPOLYMER or Z-CHLORO-ALLYL ACETATE AND ACRYLIC Acrn ExAMrLE 9.COPOLYMER or Z-CHLoRO-ALLYL ACETATE AND MErHYL ME'rHAcaYLArE A solution of 13.45'g. of2-chloroallyl acetate, 10 g. of methyl methacrylate, and 0.12 g. of benzoyl peroxide was prepared and sealed into a glass tube. The tube and contents "were heated in a water bath at 50 C'. for seventeen days, at the end of which time the product was hazy and' faintly yellow.
  • the copolymer was dissolved in acetone, the solution filteredgaj'nd the copolymer precipitated into water and soaked several hours in fresh water. It was then, steamed for four hours, redissolved in acetone, precipitated into distilled water, and soaked'in, fresh distilled water. The product was dried-.,in the air at room temperature.
  • the colorless, friable material weighed 17.2 g. and contained 11.97% of chlorine.
  • EXAMPLE 10 --CoPoLY1 ⁇ rn-i i or"- 2-CHLoao-ALLYL ACETATE AND 1STYRENE
  • a solution of 13.45 g. of 2-chloroallyl acetate, 10.4 g. of styrene, and 0.12 g, of benzoyl peroxide was prepared and'sealed into a glass tube. The tube and contents were heated in a water bath at 50 C. for twenty-one days, at the end of which time the product. was very viscous, clear, and yellow in color. It was dissolved in dioxane, poured into distilled water, steamed for four hours, and redissolved in dioxane. This solution was precipitated into distilled water, the copolymer soaked'for three hours, filtered, and dried in the air at room temperature. The colorless, friable product weighed 12.4 g. and contained 7.42% of chlorine.
  • Z-CHLORO-ALLYL ACETATE COPOLYMERS 26 acrylic acid, 10.7 0. 077 100, 16.6 hr 13. 67 1:1. 46 methyl acryiate. 12.8 0. 078 100, 3 days 13. 48 1:1. 6 13. 6 methyl acryiate, 17.2 0. 07 100, 2 days 9. 68 1:2. 76

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US442453A 1942-05-11 1942-05-11 Copolymers of 2-halogeno-allyl alcohol or 2-halogeno-allyl esters Expired - Lifetime US2419221A (en)

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US442453A US2419221A (en) 1942-05-11 1942-05-11 Copolymers of 2-halogeno-allyl alcohol or 2-halogeno-allyl esters
FR940678D FR940678A (fr) 1942-05-11 1946-12-27 Nouveaux copolymères des esters carboxyliques de 2-halogénoallyle

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2498099A (en) * 1946-04-19 1950-02-21 Us Rubber Co Interpolymers of styrene, fumaric esters, and chlorinated alkenes
US2498084A (en) * 1946-04-19 1950-02-21 Us Rubber Co Interpolymers of fumaric esters and a chlorinated alkene
US2557189A (en) * 1947-01-10 1951-06-19 Celanese Corp Copolymers of unsaturated esters
US2563611A (en) * 1951-08-07 Phen ylallyl alcohol
US2600421A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers of acrylates and allyl esters
US2600383A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers from allyl esters and methacrylic esters
US2600448A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers from allyl esters and acrylic esters
US2600414A (en) * 1947-08-22 1952-06-17 William C Mast Vulcanization of acrylic resins
US2600446A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers of methacrylates and allyl esters
US2951831A (en) * 1955-12-05 1960-09-06 Monsanto Chemicals Terpolymer of a conjugated diolefin, a styrene, and an allyl alcohol
US3245954A (en) * 1961-04-05 1966-04-12 Shell Oil Co Hydroxy-containing polymers of mesityl oxides

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160941A (en) * 1938-04-01 1939-06-06 Dow Chemical Co Vinylidene chloride co-polymers
US2160943A (en) * 1938-05-02 1939-06-06 Dow Chemical Co Vinylidene chloride co-polymers
US2186360A (en) * 1938-02-23 1940-01-09 Dow Chemical Co Styrene copolymers
US2205390A (en) * 1938-06-10 1940-06-25 Dow Chemical Co Copolymers of styrene and 2-chloroallyl esters
GB540168A (en) * 1938-12-30 1941-10-08 American Cyanamid Co Resinous compositions and methods of preparing same
US2273891A (en) * 1939-02-18 1942-02-24 Pittsburgh Plate Glass Co Method of polymerizing polymerizable materials containing more than one polymerizable grouping
US2308495A (en) * 1939-10-31 1943-01-19 Gen Electric Interpolymerization product of an unsaturated alkyd resin and a monoallyl ester of anonvinylic monoesterifiable acid
US2332460A (en) * 1939-08-10 1943-10-19 Pittsburgh Plate Glass Co Polymerized esters of polymeric unsaturated alcohols and method of manufacture thereof
US2332897A (en) * 1940-06-07 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed, acetalized, and/or ketalized copolymers of vinyl esters and unsaturated ketones containing at least one ch=c grouping
US2332900A (en) * 1940-07-23 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed, acetalized, and/or ketalized polymers of allyl esters
US2334358A (en) * 1938-11-16 1943-11-16 American Enka Corp Artificial cellulosic filament delustered with titanium salt
US2388851A (en) * 1942-05-11 1945-11-13 Eastman Kodak Co Soluble material which becomes insoluble upon separation from solvent

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186360A (en) * 1938-02-23 1940-01-09 Dow Chemical Co Styrene copolymers
US2160941A (en) * 1938-04-01 1939-06-06 Dow Chemical Co Vinylidene chloride co-polymers
US2160943A (en) * 1938-05-02 1939-06-06 Dow Chemical Co Vinylidene chloride co-polymers
US2205390A (en) * 1938-06-10 1940-06-25 Dow Chemical Co Copolymers of styrene and 2-chloroallyl esters
US2334358A (en) * 1938-11-16 1943-11-16 American Enka Corp Artificial cellulosic filament delustered with titanium salt
GB540168A (en) * 1938-12-30 1941-10-08 American Cyanamid Co Resinous compositions and methods of preparing same
US2273891A (en) * 1939-02-18 1942-02-24 Pittsburgh Plate Glass Co Method of polymerizing polymerizable materials containing more than one polymerizable grouping
US2332460A (en) * 1939-08-10 1943-10-19 Pittsburgh Plate Glass Co Polymerized esters of polymeric unsaturated alcohols and method of manufacture thereof
US2308495A (en) * 1939-10-31 1943-01-19 Gen Electric Interpolymerization product of an unsaturated alkyd resin and a monoallyl ester of anonvinylic monoesterifiable acid
US2332897A (en) * 1940-06-07 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed, acetalized, and/or ketalized copolymers of vinyl esters and unsaturated ketones containing at least one ch=c grouping
US2332900A (en) * 1940-07-23 1943-10-26 Gen Electric Synthetic composition comprising hydrolyzed, acetalized, and/or ketalized polymers of allyl esters
US2388851A (en) * 1942-05-11 1945-11-13 Eastman Kodak Co Soluble material which becomes insoluble upon separation from solvent

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2563611A (en) * 1951-08-07 Phen ylallyl alcohol
US2498099A (en) * 1946-04-19 1950-02-21 Us Rubber Co Interpolymers of styrene, fumaric esters, and chlorinated alkenes
US2498084A (en) * 1946-04-19 1950-02-21 Us Rubber Co Interpolymers of fumaric esters and a chlorinated alkene
US2557189A (en) * 1947-01-10 1951-06-19 Celanese Corp Copolymers of unsaturated esters
US2600414A (en) * 1947-08-22 1952-06-17 William C Mast Vulcanization of acrylic resins
US2600421A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers of acrylates and allyl esters
US2600383A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers from allyl esters and methacrylic esters
US2600448A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers from allyl esters and acrylic esters
US2600446A (en) * 1949-07-15 1952-06-17 Rohm & Haas Copolymers of methacrylates and allyl esters
US2951831A (en) * 1955-12-05 1960-09-06 Monsanto Chemicals Terpolymer of a conjugated diolefin, a styrene, and an allyl alcohol
US3245954A (en) * 1961-04-05 1966-04-12 Shell Oil Co Hydroxy-containing polymers of mesityl oxides

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