tert-butyl ethaneperoxoate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a three liter, four necked, round bottomed flask equipped with a stirrer, thermometer, condenser and addition funnel is charged 600 g. of xylene. The flask contents are heated to 139°-140° C. while a monomer mixture of 225 g. maleic anhydride, 1275 g. butyl acrylate and 60 g. of 75% t-butyl peracetate is fed at a uniform rate over a period of 31/4 hours. The reaction mixture is held at 140° C. for 15 minutes and then chased with 6.0 g. of 75% t-butyl peracetate dissolved in 40 g. of xylene fed over 45 minutes. The reaction flask is equipped with a Dean-Stark apparatus and azeotroped to dryness - (18.6 g. of water and toluene is removed). The product contains 72.2% solids with a viscosity of 205 cps. A sample is stripped to 99.4% solids and has a viscosity of 272,000 cps. No maleic anhydride could be detected in the final product and the polymer is found to have a number average molecular weight of 1500; anhydride functionality of 2.3 To a three liter, four necked, round bottomed flask equipped with a stirrer thermometer, condenser and addition funnel is charged 600 g The flask contents are heated to 139°-140° C. while a monomer mixture of 225 g The reaction flask is equipped with a Dean-Stark apparatus azeotroped to dryness - (18.6 g. of water and toluene is removed)

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a polymerization reactor equipped with an agitator and a reflux condenser were charged 580 grams of styrene, 3.0 grams of terpenolene and 200 ml of ethylbenzene. Then 80 grams of high cis-polybutadiene from Goodyear Tire & Rubber Company (Budene 1208) was dissolved in the mixture. After the rubber had dissolved, a solution of 40 grams of acrylic acid in 60 ml of methyl ethyl ketone (335 ml) was introduced into the mixture. The temperature of the reaction mixture was raised to 85° C. and maintained at this level during the ensuing polymerization. Polymerization was initiated by introducing into the system a mixture of 0.2 ml of tert-butyl peracetate and 0.2 ml of tert-butyl per-neo-decanoate. One hour later, continuous addition of a solution of 40 grams of acrylic acid and 60 ml of methyl ethyl ketone was initiated and this addition was continued over a four hour period. At one hour and again at four hours after the start of the continuous addition of the acrylic acid solution, additional 0.2 ml portions of tert-butyl peracetate were introduced into the polymerization mixture. Polymerization was terminated 5.5 hours after initiation and the resultant polymer was recovered and dried, first in air and then in a vacuum oven, to yield 432 grams of rubber-modified styrene-acrylic acid graft copolymer. In order to produce enough copolymer for the compounding and ensuing test work this polymerization procedure was repeated four more times and the products from the five runs were combined and mixed in a Waring blender. The resultant polymer contained about 84.2 weight percent styrene and about 15.8 weight percent acrylic acid. Its rubber content was approximately 18.5 percent based on the weight of the resin phase. Into a polymerization reactor equipped with an agitator and a reflux condenser After the rubber had dissolved maintained at this level during the ensuing polymerization Polymerization by introducing into the system this addition At one hour were introduced into the polymerization mixture Polymerization was terminated 5.5 hours after initiation the resultant polymer was recovered dried, first in air

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a polymerization reactor equipped with an agitator and a reflux condenser were charged 580 grams of styrene, 3.0 grams of terpenolene and 200 ml of ethylbenzene. Then 80 grams of high cis-polybutadiene from Goodyear Tire & Rubber Company (Budene 1208) was dissolved in the mixture. After the rubber had dissolved, a solution of 40 grams of acrylic acid in 60 ml of methyl ethyl ketone (335 ml) was introduced into the mixture. The temperature of the reaction mixture was raised to 85° C. and maintained at this level during the ensuing polymerization. Polymerization was initiated by introducing into the system a mixture of 0.2 ml of tert-butyl peracetate and 0.2 ml of tert-butyl per-neo-decanoate. One hour later, continuous addition of a solution of 40 grams of acrylic acid and 60 ml of methyl ethyl ketone was initiated and this addition was continued over a four hour period. At one hour and again at four hours after the start of the continuous addition of the acrylic acid solution, additional 0.2 ml portions of tert-butyl peracetate were introduced into the polymerization mixture. Polymerization was terminated 5.5 hours after initiation and the resultant polymer was recovered and dried, first in air and then in a vacuum oven, to yield 432 grams of rubber-modified styrene-acrylic acid graft copolymer. In order to produce enough copolymer for the compounding and ensuing test work this polymerization procedure was repeated four more times and the products from the five runs were combined and mixed in a Waring blender. The resultant polymer contained about 84.2 weight percent styrene and about 15.8 weight percent acrylic acid. Its rubber content was approximately 18.5 percent based on the weight of the resin phase. Into a polymerization reactor equipped with an agitator and a reflux condenser After the rubber had dissolved maintained at this level during the ensuing polymerization Polymerization by introducing into the system this addition At one hour were introduced into the polymerization mixture Polymerization was terminated 5.5 hours after initiation the resultant polymer was recovered dried, first in air

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Similar beneficial improvements in the conversion of monomer and physical properties of the polymer are obtained when the 1,1-bis(t-butyl peroxy)cyclohexane is replaced with 1,1-bis(t-butyl peroxy), 3,3,5-trimethylcyclohexane, 2,2-bis(t-butyl peroxy)butane and 2,2-bis(t-butyl peroxy)hexane. Slightly inferior results are obtained when t-butyl perbenzoate and t-butyl peracetate are employed. Slightly inferior results

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 1-liter, four-necked, round bottomed flask equipped with a mechanical stirrer, two addition funnels, a distillation head with a variable takeoff, a thermometer, a nitrogen inlet, and a heating mantle atop a thermosensor-controlled pot lifter is charged with 300 g of propylene glycol. This heel charge is heated to 150° C. under nitrogen. The monomer charge (135 g styrene, 165 g methacrylic acid, and 3 g mercaptoethanol) is gradually charged over 5 hours. Simultaneously, the initiator solution (9.0 g of 70% t-butyl peracetate) is added over the same period. After completion of the feeds, an additional 0.9 g of t-butyl peracetate solution is added and the batch held at150° C. for another hour. A 1-liter, four-necked, round bottomed flask equipped with a mechanical stirrer two addition funnels This heel charge is gradually charged over 5 hours for another hour

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a three liter, four necked, round bottomed flask equipped with a stirrer, thermometer, condenser and addition funnel is charged 600 g. of xylene. The flask contents are heated to 139°-140° C. while a monomer mixture of 225 g. maleic anhydride, 1275 g. butyl acrylate and 60 g. of 75% t-butyl peracetate is fed at a uniform rate over a period of 31/4 hours. The reaction mixture is held at 140° C. for 15 minutes and then chased with 6.0 g. of 75% t-butyl peracetate dissolved in 40 g. of xylene fed over 45 minutes. The reaction flask is equipped with a Dean-Stark apparatus and azeotroped to dryness - (18.6 g. of water and toluene is removed). The product contains 72.2% solids with a viscosity of 205 cps. A sample is stripped to 99.4% solids and has a viscosity of 272,000 cps. No maleic anhydride could be detected in the final product and the polymer is found to have a number average molecular weight of 1500; anhydride functionality of 2.3 To a three liter, four necked, round bottomed flask equipped with a stirrer thermometer, condenser and addition funnel is charged 600 g The flask contents are heated to 139°-140° C. while a monomer mixture of 225 g The reaction flask is equipped with a Dean-Stark apparatus azeotroped to dryness - (18.6 g. of water and toluene is removed)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In Example 5, the t-butyl peroxybenzoate was replaced by 5 ml of t-butyl peroxyacetate (30% solution), whereby 0.60 g of 2-cyclohexenyl acetate was obtained.

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Blend C Copolymer--Into a polymerization reactor equipped with an agitator and a reflux condenser were charged 770 ml of styrene, 4 grams of terpinolene, 200 ml of ethylbenzene and 200 ml of methyl ethyl ketone. Then 100 grams of medium cis-polybutadiene from Firestone Tire & Rubber Company (Diene 35) was dissolved in the mixture. After the rubber had dissolved, 50 ml of acrylic acid was added to the mixture. The temperature of the reaction mixture was raised to 80° C. and maintained between 80° and 120° C. during the course of the polymerization. Polymerization was initiated by introducing into the system a mixture of 0.3 ml of tert-butyl peracetate and 0.3 ml of tert-butyl per-neo-decanoate. About 1.5 hours later, continuous addition of 50 ml of acrylic acid was initiated and this addition was continued for about 5 hours. Additional 0.3 ml portions of tert-butyl peracetate were introduced into the polymerization mixture at 135 minutes and 270 minutes after the initiation of polymerization. To control the viscosity of the reaction mixture, 350 ml of methyl ethyl ketone was added from 315 minutes to 390 minutes after initiation of polymerization. Polymerization was terminated about 6.75 hours after initiation and a solution of two grams of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene and 0.5 gram of tris(nonylphenyl)phosphite dissolved in 100 ml of methyl ethyl ketone was added. The resultant polymer was recovered and dried, first in air and then in a vacuum oven, to yield 660 grams of rubber-modified styrene-acrylic acid graft copolymer. The resultant polymer contained about 85.6% styrene and about 14.4% acrylic acid. Its rubber content was approximately 15.1% based on the weight of the resin phase. Blend C Copolymer--Into a polymerization reactor equipped with an agitator and a reflux condenser After the rubber had dissolved maintained between 80° and 120° C. during the course of the polymerization Polymerization by introducing into the system this addition was continued for about 5 hours after the initiation of polymerization was added from 315 minutes to 390 minutes after initiation of polymerization Polymerization was terminated about 6.75 hours after initiation a solution of two grams of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene and 0.5 gram of tris(nonylphenyl)phosphite dissolved in 100 ml of methyl ethyl ketone was added The resultant polymer was recovered dried, first in air

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Blend B Copolymer--Into a polymerization reactor equipped with an agitator and a reflux condenser were charged 616 ml of styrene, 3.0 grams of terpinolene and 200 ml of ethylbenzene. Then 80 grams of high cis-polybutadiene from Goodyear Tire & Rubber Company (Budene 1208) was dissolved in the mixture. After the rubber had dissolved, a solution of 40 grams of acrylic acid in 60 ml of methyl ethyl ketone was introduced into the mixture. The temperature of the reaction mixture was raised to 95° C. and maintained between 95° and 120° C. during the course of the polymerization. Polymerization was initiated by introducing into the system a mixture of 0.2 ml of tert-butyl peracetate and 0.2 ml of tert-butyl per-neo-decanoate. About one hour later, continuous addition of a solution of 40 grams of acrylic acid and 60 ml of methyl ethyl ketone was initiated and this addition was continued for about 4.5 hours. Additional 0.2 ml portions of tert-butyl peracetate were introduced into the polymerization mixture at 110 minutes and 310 minutes after the initiation of polymerization. Polymerization was terminated 5.5 hours after initiation and the resultant polymer was recovered and dried, first in air and then in a vacuum oven, to yield 432 grams of rubber-modified styrene-acrylic acid graft copolymer. In order to produce enough copolymer for the ensuing test work this general procedure was repeated five more times and the products from the six runs were combined and mixed in a Waring blender. Variations in the polymerization conditions occurred from run to run but were not of material significance. The resultant combined polymer contained about 84.6% styrene and about 15.4% acrylic acid. Its rubber content was approximately 17.1% based on the weight of the resin phase. Blend B Copolymer--Into a polymerization reactor equipped with an agitator and a reflux condenser After the rubber had dissolved maintained between 95° and 120° C. during the course of the polymerization Polymerization by introducing into the system this addition was continued for about 4.5 hours after the initiation of polymerization Polymerization was terminated 5.5 hours after initiation the resultant polymer was recovered dried, first in air

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a polymerization reactor equipped with an agitator and a reflux condenser were charged 580 grams of styrene, 3.0 grams of terpenolene and 200 ml of ethylbenzene. Then 80 grams of high cis-polybutadiene from Goodyear Tire & Rubber Company (Budene 1208) was dissolved in the mixture. After the rubber had dissolved, a solution of 40 grams of acrylic acid in 60 ml of methyl ethyl ketone (335 ml) was introduced into the mixture. The temperature of the reaction mixture was raised to 85° C. and maintained at this level during the ensuing polymerization. Polymerization was initiated by introducing into the system a mixture of 0.2 ml of tert-butyl peracetate and 0.2 ml of tert-butyl per-neo-decanoate. One hour later, continuous addition of a solution of 40 grams of acrylic acid and 60 ml of methyl ethyl ketone was initiated and this addition was continued over a four hour period. At one hour and again at four hours after the start of the continuous addition of the acrylic acid solution, additional 0.2 ml portions of tert-butyl peracetate were introduced into the polymerization mixture. Polymerization was terminated 5.5 hours after initiation and the resultant polymer was recovered and dried, first in air and then in a vacuum oven, to yield 432 grams of rubber-modified styrene-acrylic acid graft copolymer. In order to produce enough copolymer for the compounding and ensuing test work this polymerization procedure was repeated four more times and the products from the five runs were combined and mixed in a Waring blender. The resultant polymer contained about 84.2 weight percent styrene and about 15.8 weight percent acrylic acid. Its rubber content was approximately 18.5 percent based on the weight of the resin phase. Into a polymerization reactor equipped with an agitator and a reflux condenser After the rubber had dissolved maintained at this level during the ensuing polymerization Polymerization by introducing into the system this addition At one hour were introduced into the polymerization mixture Polymerization was terminated 5.5 hours after initiation the resultant polymer was recovered dried, first in air