CA1098637A - Preparation of block copolymers and products therefrom - Google Patents
Preparation of block copolymers and products therefromInfo
- Publication number
- CA1098637A CA1098637A CA298,867A CA298867A CA1098637A CA 1098637 A CA1098637 A CA 1098637A CA 298867 A CA298867 A CA 298867A CA 1098637 A CA1098637 A CA 1098637A
- Authority
- CA
- Canada
- Prior art keywords
- block
- styrene
- monomer
- copolymer
- acrylonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Block copolymers of AB or ABA configuration are prepared by anionically polymerizing one component, terminating the living polymer with sulfur or an episulfide and completing polymerization of the remaining block portion by free-radical polymerization.
By this process one can prepare block copolymers con-taining monomers which are generally considered unsuitable for anionic polymerization.
18,312-F
18,312-F
Block copolymers of AB or ABA configuration are prepared by anionically polymerizing one component, terminating the living polymer with sulfur or an episulfide and completing polymerization of the remaining block portion by free-radical polymerization.
By this process one can prepare block copolymers con-taining monomers which are generally considered unsuitable for anionic polymerization.
18,312-F
18,312-F
Description
This inven-tion provides an improved process for the preparation of block copolymers which permits the inclusion of monomers which are generally considered unsuitable for anionic polymerization and block copolymers containing such monomers.
The present invention resides in a process for the preparation of a block copolymer comprising pro-viding an anionicall.y polymerizable monomer or mixtures thereof, polymerizing the monomer or mixture thereof anionically to provide polymer chains having at least one living end, contacting said polymer chains with elemental sulfur or an episulfide having the formula R-CH~CH2 \/
wherein R is hydrogen, an aromatic group or an alkyl group containing 1 to 18 carbons in a quan~ity at least sufficient to react with said polymer chain living ends, ; to thereby terminate the ends with a primary or secondary ; thiol group, characterized by contacting the thiol termi-` 20 nated polymer chains with a free-radical polymerizable monomer and initiating free-radical polymerization to thereby provide a block copolymer comprising at least one anionically polymerized block and at least one free~
-radical initiated block.
.
.: 25 Also within the scope of the present invention are block copolymers prepared in accordance with the method of the invention.
Monomers which are polymerizable by free-: -radical initiation suitable for the practice of the `~ 30 present in~ention include; for example, p-chlorostyrene, :
~8,312-F
i37 bromostyrene, acrylonitrile, methacrylonitrile and acrylates and methacrylates.
By the term "sulfur-compound" is meant elemental sulfur and alkyl episulfides, the epi-sulfides being of the formula:
' ' ' ' , .
, . :
, -.
18,312-F -la-: :.
: '~ '. - .
63~7 R-CII-CII
~ ~ 2 wherein R is hydrogen, lower alkyl (1-18 carbon atoms) and aromatic group contains only hydrogen and carbon.
Such compounds include; for example, ethylene sulfide, propylene episulfide, dodecylene episulEide, and phenyl episulfide.
Solvents normally used in anionic polymeriza~
tion can be employed in accordance with the present invention.
The organolithium compounds used correspond to the formula R(Li)X, wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical and x is an integer from 1 to 4, inclusive. The aliphatic and cycloaliphatic radicals can be saturated or contain olefinic unsaturation. The R in the formula has a valence equal to the integer, and preferably contains from 1 to 20 incluslve, carbon atoms, although it is within the scope of the invention to use higher molecular weight compounds.
The preferred compound is n-butyllithium.
Another desirable variety of li-thium , initiators are the difunctional llthium compounds such ; ~ as are described in German Application No. P 26.34,391.9 filed July 30, 1976.
Lithium compounds are used with particular 2S~ benefit, however, other known alkaIi metal anionic polymerization initiating systems may be used if desired.
The amount of catalyst or initiator used in the preparation of block copolymers by anionic poly- -merization can vary over a wide range but will ~ .
: ~ :
18,312-F -2-3"~
generally be a-t least 0.00001 mole of the organo-lithium compound per 100 moles of the total monomers to be polymerized in the process. The upper limit for the amount of organolithium used depends primarily upon catalyst solubility and the desired molecular weight of the polymer rcsulting from the polymerization. A
preferred effective catalyst level is Erom 0.005 to l mole of organoli-thium per 100 moles oE total monomers charged to the polymerization zone.
In the free-radical polymerization in accordance with the invention, many free-radical polymerization initiating compounds may be employed or alternatively free radicals may be generated by heating in the absence of a peroxide compound or other free-radical generating compound.
The free-radical generating compounds which can be employed in this invention include organic, inorganic peroxides and azo compounds. The term "organic peroxides" is meant to include the hydro-peroxides, unlPss otherwise stated, and to encompass ; compounds containing from 4 to 40 carbon atoms per molecule, inclusive. The organic peroxides can also be substituted with non-peroxy members such as halogen, hydroxy radicals, Pther and/or ester linkages.
The free-radical polymerization in accordance with the invention may be carried out in solution sus-pension, bulk or emulsion techniques. A wide variety of block copolymers may be readily prepared by the process of the present invention. Such polymers may ~30 have homopolymer blocks, copolymer blocks or a mixed , ' ' 18,312-F ` _3_ ~
3Lq36~3 6i3~
block co~olymer wherein one oE the bloc]cs may be ~
homopolymer and one or more of -the blocks bein~ co~olymer.
Particularly desirable block copolymers in accordance with the present invention are an ABA co-polymer of butadiene and a random copolymer of styrene and acrylonitrile. By -the term "random copolymer'l is meant one wherein the sequence of styrene and acrylo-nitrile does not have a precise,mathematical relation-ship. Beneficially, the block B is a homopolymer of butadiene or isoI~rene having a molccular we:ight of 30,000 to 500,000 and preferably 40,000 -to 80,000, the A block containing 95 to 50 parts by weight styrene and 5 to 50 parts by weight of acrylonitrile, the A
block having a weight average molecular weight of from 3,000 to 100,000 and preferably 5,000 to 20,000 molecular weight units, as determined by gel permeation chromato-graphy. Another desirable block copolymer of the ABA
' configuration is a block copolymer of butadiene or isoprene with bromostyrene wherein the block B has the hereinbefore delineated molecular weight limitations and - block A is a bromostyrene block having a weight average ;~ ~ molecular weight of 5,000 to 200,000 and beneficially' from 10,000 to'50,000 molecular weight units, the molecular ~ weight being determined by gel permeation chromatography.
;~ 25 Polymers prepared in accordance with the present invention beneficially can be employed for a variety of ~; applications by selection of the desired ~locks.
Thermoplastic elastomers~are readily prepared as well as thermoplastics, po1ymeric surface active asents, emulsiflers, and vulcanizable elastomers. Thermoplastic ,' 18,312-F -4-: ~ ~- :- . . , 63~7 elastomers, thermoplastics and rubbers prepared in accordance with the present invention are readily fabricated by con~entional fabricating techniques such as solvent casting, compression molding~ injection molding, extrusion, melt spinning and like fabrication techniques to provide a wide variety of useful articles including fibers, films, compression molding, injection moldings, and the like. Block polymers in accordance with the present invention may be compounded with pigment, fillers, stabilizers, dyes and the like in ; conventional plastic or elastomer processing procedures.
The invention is further illustrated by the following examples.
Example 1 An agitated, nitrogen~purged flask was charged with 50 grams of butadiene dissolved in 450 milliliters of dry benzene. 14.3 Milliequivalents of n-butyllithium in benzene was added and the temperature of the reaction mixture maintained by means of a water bath at a tempera-ture of from about 50 to 55C. Polymerization was com-pleted in about thirty minutes. A 20 milliliter portion of the reaction~mixture was withdrawn from the vessel by a syringe and injected into a 100 milliliter nitrogen-purged flask whlch contained 0.15 milliliter of tetra-~25 hydrofuran. The mixture of polybutadiene solution and tetrahydrofuran was cooled to about 5~C and 0.16 milliliter of propylene sulfide added. The resultlng mixture was ætirred for about 12 minutes and 0.1 mil-liliter of glacial~acetic acid was added to the mixture and the mixture dlluted with about 60 mil]iliters .
1~,312-F ~5~
.
.
3~7 of methanol. On addition of methanol, a precipitate formed. The precipitate ~JaS scparated by fil-tration an~ dried overnigllt at roolrl t~rnl~er.lture undcr vacuum.
The product was 2 grams o~ polybutadiene with a mer-captan cap or end group. A second 20 milliliter portion of the reaction mixture was similarly treated with the exception that 0.13 milliliter of ethylene sulfide was employed in place of propylene sulfide to provide an ethylene sulfide terminated polybutadiene weighing about 2 grams. A 1/10 gram portion of the propylene sulfide terminated polybutadiene was mixed with 10 milliliters o~ styrene monomer and 5 mi]lili-ters of ethylbenzene. The mixturc was divided into two portions and each portion was placed in a glass ampoule. Both ampoules were heated to 125C, one ampoule for a period of one hour and the remaining ampoule for three hours.
At the end of that time, the ampoules were cooled, the contents removed and analyzed by gel permeation chroma-tography. The weight of the polymer sample recovered showed that at the end of one hour heating, 7.5 weight percent of the styrene polyrnerized and the sample heated for three hours resulted in 22.5 weight percent polymerized styrene. Gel permeation chromatography chromatograms indicated the presence of some mercaptan capped poly-25~ butadiene in the sample which had been heated for one hour. No indication of the mercaptan capped poly-butadiene was present in the sample which had been :
heated for~three~hours. Similar results were obtained with the ethylene sulfide terminated polybutadiene.
`: : :
A portion of the~polybutadiene solution which was ~: :: , :
~18,~312-F ` -6-. . , . .. . ~
~9~3~3~
uncapped was termlna-ted with glacial acetic acid and subsequently subjected to the same polymerizing con-dition, that is, 125C for one hour and for three hours in the presence of styrene and on examination using gel permeation chromatography, the peak corresponding to the polybutadiene appeared gen~erally unchanged. The foregoing demonstrate clearly that the sulfide-terminated polymers exhibit a strong tendency to form block copolymers.
The block copolymers prepared were of the AB configuration.
Example 2 A quantity of bis[4~ phenylethenyl)phenyl]-ether (0.4 gram) in 30 milliliters of dry benzene was mixed with 2.36 milliequivalents of secondary butyl lithium at room temperature for a period of three hours to form oxydi-4,1-phenylene bis(3-methyl-1-phenylpentyl-idene)-bis(lithium). To the reaction vessel was added two milliliters of isoprene, and the reaction mixture - heated for about 5 minutes at 60C, thereby solubilizing the suspension of the bislithium compound. The resulting solution was then charged to a one-liter nitrogen purged flask which contained 40 grams of butadiene dissolved -~ in 450 milliliters of dry benzene. A water bath having a temperature between about 50 and 55C was employed to maintain the témperature of the reaction mixture.
Polymerization of the butadiene proceeded for a~out 55 minutes and the reaction vessel and mixture cooled in an ice bath. A solution of one-hal milliliter of propy-lene sulfide and two milliliters of te-trahydrofuran were added to the vessel with agitation. The viscosity of the reaction mixture appeared to decrease somewhat and : : . :
18,312~F ~ -7--~ ~9~3Ç;37 then increase rapidly. Fifteen minutes after the addition of the propylene sulfide, one milliliter of glacial acetic acid was added to terminate any active anions. The yield of the dimercaptan capped poly-butadiene was quantitative. The cappe~ polybutadiene had an inheren-t viscosity of 0.79 deciliter per gram when measured in toluene at 0.15 gram of polymer per one-hundred milliliters oE toluene at a temperature of 25C. Eight grams of the capped polybutadiene were mixed with 21 grams of bromostyrene, 0.2 gram o~ azo-bisisobutyrolnitrile and 37 grams ethylbenzene. The resulting mixture was placed in a nitrogen purged, closed, stainless steel tube and heated to 70C and maintained at that temperature for a period of six hours. The polymer was recovered by dissolving reaction mixture in benzene and precipitation in methanol. Upon molding of the resultant thermoplastic elastomeric polymer, the tensile strength at rupture was 1620 pounds per square inch (123 kg/sq cm) with an ultimate elonga-tion of 520 percent.
Example 3 A block copolymer was prepared in the following manner. A dry toluene solution containing 0.26 gram of bis[4-(1-phenylethenyl)phenyl] ether in 20 milli-.
liters of to]uene was mixed with 1.5 milliequivalents of sec-butyl3ithlum at room temperature for a period of 65 minutes. The reac~tion mixture was a toluene ~. ,.,: :
dispersion of oxydi~4,1-phenylene bis(3-methyl-1--phenylpentylidene)-bis(lithium). To the toluene dispersion was added 1.3 milliliters of isoprene and 18,312-F ~ ~8-': ~ ~ : ~ , . , . ........................ ,' . .
.
~8~3~7 the mixture hea-ted -to 60C for a period of 5 minu-tes.
The dispersion became a solution as the isoprene was added to the bisli-thium com~o~lnd. The resul-ting solu-tion of the sol~bilized bislithium compound was charged to a one-liter nitrogen purged flask which contained 450 milliliters of dry toluene having dis-solved therein 40 grams of butadiene. The butadiene solution in the reaction flask was previously treated with 0.31 milliequivalent of sec-butyllithium for the purpose of removing active impurities such as oxygen and moisture which are known to interfere with the polymerization reaction. The charged one-liter flask was position~d in a water bath maintained at a temperature of about 55 for a period of about 90 lS minutes. At the end of the 90 minute period, poly-merization was assumed complete. The one-liter flask and contents were placed in an ice bath for a period of about 10 minutes. At the end of this period of time, the temperature of the reaction mixture as determined by the use of a ther couple in the flask was about 30C. A one-half milliliter portion of purified propylene sulfide and a 2 milliliter portion , of purified tetrahydrofuran were added to the flask.
Twenty minutes after the addition of the propylene sulfide and tetrahydrofuran, 0.12 milliliter of glacial `~ ~ acetic acid was added to the flask to terminate the active llthium sltes. The reaction mixture contained a dimercaptan capped polybutadiene and the solution wàs malntained;at about room temperature overnlght.
The following morn1ng, 33 millillters of styrene, :::
`
~ 18,312-F ~ g ~ ~ .
12.5 milliliters of acrylonitrile and 1.63 grams of azobisiso~utyrolnitrile were added to the reaction mixture in the one-liter flask. The reaction mixture was then heated to 70C for a period of five hours with continuous stirring. At the end of this period, a polymeric product was separated from the reaction mixture, 57 grams of a thermoplastic elastomeric polymer was recoveredO A portion of the polymer was molded and the tensile strength at break was determined to be 1124 pounds per square inch (78.7 kg/sq cm). The elongation at break was 460 percent. A compression molded film was analyzed employing infrared spectroscopy. The analysis indicated that the polymer contained about 16.7 weight percent styrene, 6.4 weight percent acrylonitrile, and about 76.9 percent butadiene.
' : :
: ~ .
18,312-F 10- .
~: .
::
~ . - ,
The present invention resides in a process for the preparation of a block copolymer comprising pro-viding an anionicall.y polymerizable monomer or mixtures thereof, polymerizing the monomer or mixture thereof anionically to provide polymer chains having at least one living end, contacting said polymer chains with elemental sulfur or an episulfide having the formula R-CH~CH2 \/
wherein R is hydrogen, an aromatic group or an alkyl group containing 1 to 18 carbons in a quan~ity at least sufficient to react with said polymer chain living ends, ; to thereby terminate the ends with a primary or secondary ; thiol group, characterized by contacting the thiol termi-` 20 nated polymer chains with a free-radical polymerizable monomer and initiating free-radical polymerization to thereby provide a block copolymer comprising at least one anionically polymerized block and at least one free~
-radical initiated block.
.
.: 25 Also within the scope of the present invention are block copolymers prepared in accordance with the method of the invention.
Monomers which are polymerizable by free-: -radical initiation suitable for the practice of the `~ 30 present in~ention include; for example, p-chlorostyrene, :
~8,312-F
i37 bromostyrene, acrylonitrile, methacrylonitrile and acrylates and methacrylates.
By the term "sulfur-compound" is meant elemental sulfur and alkyl episulfides, the epi-sulfides being of the formula:
' ' ' ' , .
, . :
, -.
18,312-F -la-: :.
: '~ '. - .
63~7 R-CII-CII
~ ~ 2 wherein R is hydrogen, lower alkyl (1-18 carbon atoms) and aromatic group contains only hydrogen and carbon.
Such compounds include; for example, ethylene sulfide, propylene episulfide, dodecylene episulEide, and phenyl episulfide.
Solvents normally used in anionic polymeriza~
tion can be employed in accordance with the present invention.
The organolithium compounds used correspond to the formula R(Li)X, wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical and x is an integer from 1 to 4, inclusive. The aliphatic and cycloaliphatic radicals can be saturated or contain olefinic unsaturation. The R in the formula has a valence equal to the integer, and preferably contains from 1 to 20 incluslve, carbon atoms, although it is within the scope of the invention to use higher molecular weight compounds.
The preferred compound is n-butyllithium.
Another desirable variety of li-thium , initiators are the difunctional llthium compounds such ; ~ as are described in German Application No. P 26.34,391.9 filed July 30, 1976.
Lithium compounds are used with particular 2S~ benefit, however, other known alkaIi metal anionic polymerization initiating systems may be used if desired.
The amount of catalyst or initiator used in the preparation of block copolymers by anionic poly- -merization can vary over a wide range but will ~ .
: ~ :
18,312-F -2-3"~
generally be a-t least 0.00001 mole of the organo-lithium compound per 100 moles of the total monomers to be polymerized in the process. The upper limit for the amount of organolithium used depends primarily upon catalyst solubility and the desired molecular weight of the polymer rcsulting from the polymerization. A
preferred effective catalyst level is Erom 0.005 to l mole of organoli-thium per 100 moles oE total monomers charged to the polymerization zone.
In the free-radical polymerization in accordance with the invention, many free-radical polymerization initiating compounds may be employed or alternatively free radicals may be generated by heating in the absence of a peroxide compound or other free-radical generating compound.
The free-radical generating compounds which can be employed in this invention include organic, inorganic peroxides and azo compounds. The term "organic peroxides" is meant to include the hydro-peroxides, unlPss otherwise stated, and to encompass ; compounds containing from 4 to 40 carbon atoms per molecule, inclusive. The organic peroxides can also be substituted with non-peroxy members such as halogen, hydroxy radicals, Pther and/or ester linkages.
The free-radical polymerization in accordance with the invention may be carried out in solution sus-pension, bulk or emulsion techniques. A wide variety of block copolymers may be readily prepared by the process of the present invention. Such polymers may ~30 have homopolymer blocks, copolymer blocks or a mixed , ' ' 18,312-F ` _3_ ~
3Lq36~3 6i3~
block co~olymer wherein one oE the bloc]cs may be ~
homopolymer and one or more of -the blocks bein~ co~olymer.
Particularly desirable block copolymers in accordance with the present invention are an ABA co-polymer of butadiene and a random copolymer of styrene and acrylonitrile. By -the term "random copolymer'l is meant one wherein the sequence of styrene and acrylo-nitrile does not have a precise,mathematical relation-ship. Beneficially, the block B is a homopolymer of butadiene or isoI~rene having a molccular we:ight of 30,000 to 500,000 and preferably 40,000 -to 80,000, the A block containing 95 to 50 parts by weight styrene and 5 to 50 parts by weight of acrylonitrile, the A
block having a weight average molecular weight of from 3,000 to 100,000 and preferably 5,000 to 20,000 molecular weight units, as determined by gel permeation chromato-graphy. Another desirable block copolymer of the ABA
' configuration is a block copolymer of butadiene or isoprene with bromostyrene wherein the block B has the hereinbefore delineated molecular weight limitations and - block A is a bromostyrene block having a weight average ;~ ~ molecular weight of 5,000 to 200,000 and beneficially' from 10,000 to'50,000 molecular weight units, the molecular ~ weight being determined by gel permeation chromatography.
;~ 25 Polymers prepared in accordance with the present invention beneficially can be employed for a variety of ~; applications by selection of the desired ~locks.
Thermoplastic elastomers~are readily prepared as well as thermoplastics, po1ymeric surface active asents, emulsiflers, and vulcanizable elastomers. Thermoplastic ,' 18,312-F -4-: ~ ~- :- . . , 63~7 elastomers, thermoplastics and rubbers prepared in accordance with the present invention are readily fabricated by con~entional fabricating techniques such as solvent casting, compression molding~ injection molding, extrusion, melt spinning and like fabrication techniques to provide a wide variety of useful articles including fibers, films, compression molding, injection moldings, and the like. Block polymers in accordance with the present invention may be compounded with pigment, fillers, stabilizers, dyes and the like in ; conventional plastic or elastomer processing procedures.
The invention is further illustrated by the following examples.
Example 1 An agitated, nitrogen~purged flask was charged with 50 grams of butadiene dissolved in 450 milliliters of dry benzene. 14.3 Milliequivalents of n-butyllithium in benzene was added and the temperature of the reaction mixture maintained by means of a water bath at a tempera-ture of from about 50 to 55C. Polymerization was com-pleted in about thirty minutes. A 20 milliliter portion of the reaction~mixture was withdrawn from the vessel by a syringe and injected into a 100 milliliter nitrogen-purged flask whlch contained 0.15 milliliter of tetra-~25 hydrofuran. The mixture of polybutadiene solution and tetrahydrofuran was cooled to about 5~C and 0.16 milliliter of propylene sulfide added. The resultlng mixture was ætirred for about 12 minutes and 0.1 mil-liliter of glacial~acetic acid was added to the mixture and the mixture dlluted with about 60 mil]iliters .
1~,312-F ~5~
.
.
3~7 of methanol. On addition of methanol, a precipitate formed. The precipitate ~JaS scparated by fil-tration an~ dried overnigllt at roolrl t~rnl~er.lture undcr vacuum.
The product was 2 grams o~ polybutadiene with a mer-captan cap or end group. A second 20 milliliter portion of the reaction mixture was similarly treated with the exception that 0.13 milliliter of ethylene sulfide was employed in place of propylene sulfide to provide an ethylene sulfide terminated polybutadiene weighing about 2 grams. A 1/10 gram portion of the propylene sulfide terminated polybutadiene was mixed with 10 milliliters o~ styrene monomer and 5 mi]lili-ters of ethylbenzene. The mixturc was divided into two portions and each portion was placed in a glass ampoule. Both ampoules were heated to 125C, one ampoule for a period of one hour and the remaining ampoule for three hours.
At the end of that time, the ampoules were cooled, the contents removed and analyzed by gel permeation chroma-tography. The weight of the polymer sample recovered showed that at the end of one hour heating, 7.5 weight percent of the styrene polyrnerized and the sample heated for three hours resulted in 22.5 weight percent polymerized styrene. Gel permeation chromatography chromatograms indicated the presence of some mercaptan capped poly-25~ butadiene in the sample which had been heated for one hour. No indication of the mercaptan capped poly-butadiene was present in the sample which had been :
heated for~three~hours. Similar results were obtained with the ethylene sulfide terminated polybutadiene.
`: : :
A portion of the~polybutadiene solution which was ~: :: , :
~18,~312-F ` -6-. . , . .. . ~
~9~3~3~
uncapped was termlna-ted with glacial acetic acid and subsequently subjected to the same polymerizing con-dition, that is, 125C for one hour and for three hours in the presence of styrene and on examination using gel permeation chromatography, the peak corresponding to the polybutadiene appeared gen~erally unchanged. The foregoing demonstrate clearly that the sulfide-terminated polymers exhibit a strong tendency to form block copolymers.
The block copolymers prepared were of the AB configuration.
Example 2 A quantity of bis[4~ phenylethenyl)phenyl]-ether (0.4 gram) in 30 milliliters of dry benzene was mixed with 2.36 milliequivalents of secondary butyl lithium at room temperature for a period of three hours to form oxydi-4,1-phenylene bis(3-methyl-1-phenylpentyl-idene)-bis(lithium). To the reaction vessel was added two milliliters of isoprene, and the reaction mixture - heated for about 5 minutes at 60C, thereby solubilizing the suspension of the bislithium compound. The resulting solution was then charged to a one-liter nitrogen purged flask which contained 40 grams of butadiene dissolved -~ in 450 milliliters of dry benzene. A water bath having a temperature between about 50 and 55C was employed to maintain the témperature of the reaction mixture.
Polymerization of the butadiene proceeded for a~out 55 minutes and the reaction vessel and mixture cooled in an ice bath. A solution of one-hal milliliter of propy-lene sulfide and two milliliters of te-trahydrofuran were added to the vessel with agitation. The viscosity of the reaction mixture appeared to decrease somewhat and : : . :
18,312~F ~ -7--~ ~9~3Ç;37 then increase rapidly. Fifteen minutes after the addition of the propylene sulfide, one milliliter of glacial acetic acid was added to terminate any active anions. The yield of the dimercaptan capped poly-butadiene was quantitative. The cappe~ polybutadiene had an inheren-t viscosity of 0.79 deciliter per gram when measured in toluene at 0.15 gram of polymer per one-hundred milliliters oE toluene at a temperature of 25C. Eight grams of the capped polybutadiene were mixed with 21 grams of bromostyrene, 0.2 gram o~ azo-bisisobutyrolnitrile and 37 grams ethylbenzene. The resulting mixture was placed in a nitrogen purged, closed, stainless steel tube and heated to 70C and maintained at that temperature for a period of six hours. The polymer was recovered by dissolving reaction mixture in benzene and precipitation in methanol. Upon molding of the resultant thermoplastic elastomeric polymer, the tensile strength at rupture was 1620 pounds per square inch (123 kg/sq cm) with an ultimate elonga-tion of 520 percent.
Example 3 A block copolymer was prepared in the following manner. A dry toluene solution containing 0.26 gram of bis[4-(1-phenylethenyl)phenyl] ether in 20 milli-.
liters of to]uene was mixed with 1.5 milliequivalents of sec-butyl3ithlum at room temperature for a period of 65 minutes. The reac~tion mixture was a toluene ~. ,.,: :
dispersion of oxydi~4,1-phenylene bis(3-methyl-1--phenylpentylidene)-bis(lithium). To the toluene dispersion was added 1.3 milliliters of isoprene and 18,312-F ~ ~8-': ~ ~ : ~ , . , . ........................ ,' . .
.
~8~3~7 the mixture hea-ted -to 60C for a period of 5 minu-tes.
The dispersion became a solution as the isoprene was added to the bisli-thium com~o~lnd. The resul-ting solu-tion of the sol~bilized bislithium compound was charged to a one-liter nitrogen purged flask which contained 450 milliliters of dry toluene having dis-solved therein 40 grams of butadiene. The butadiene solution in the reaction flask was previously treated with 0.31 milliequivalent of sec-butyllithium for the purpose of removing active impurities such as oxygen and moisture which are known to interfere with the polymerization reaction. The charged one-liter flask was position~d in a water bath maintained at a temperature of about 55 for a period of about 90 lS minutes. At the end of the 90 minute period, poly-merization was assumed complete. The one-liter flask and contents were placed in an ice bath for a period of about 10 minutes. At the end of this period of time, the temperature of the reaction mixture as determined by the use of a ther couple in the flask was about 30C. A one-half milliliter portion of purified propylene sulfide and a 2 milliliter portion , of purified tetrahydrofuran were added to the flask.
Twenty minutes after the addition of the propylene sulfide and tetrahydrofuran, 0.12 milliliter of glacial `~ ~ acetic acid was added to the flask to terminate the active llthium sltes. The reaction mixture contained a dimercaptan capped polybutadiene and the solution wàs malntained;at about room temperature overnlght.
The following morn1ng, 33 millillters of styrene, :::
`
~ 18,312-F ~ g ~ ~ .
12.5 milliliters of acrylonitrile and 1.63 grams of azobisiso~utyrolnitrile were added to the reaction mixture in the one-liter flask. The reaction mixture was then heated to 70C for a period of five hours with continuous stirring. At the end of this period, a polymeric product was separated from the reaction mixture, 57 grams of a thermoplastic elastomeric polymer was recoveredO A portion of the polymer was molded and the tensile strength at break was determined to be 1124 pounds per square inch (78.7 kg/sq cm). The elongation at break was 460 percent. A compression molded film was analyzed employing infrared spectroscopy. The analysis indicated that the polymer contained about 16.7 weight percent styrene, 6.4 weight percent acrylonitrile, and about 76.9 percent butadiene.
' : :
: ~ .
18,312-F 10- .
~: .
::
~ . - ,
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the preparation of a block copolymer comprising providing an anionically polymeri-zable monomer or mixtures thereof, polymerizing the monomer or mixture thereof anionically to provide polymer chains having at least one living end, contacting said polymer chains with elemental sulfur or an episulfide having the formula wherein R is hydrogen, an aromatic group or an alkyl group containing 1 to 18 carbons in a quantity at least sufficient to react with said polymer chain living ends, to thereby terminate the ends with a primary or secondary thiol group, characterized by contacting the thiol terminated polymer chains with a free-radical polymeri-zable monomer and initiating free-radical polymerization to thereby provide a block copolymer comprising at least one anionically polymerized block and at least one free-radical initiated block.
2. Process of Claim 1 wherein the anionically polymerized monomer is polymerized in the presence of an organic polylithium initiator.
3. Process of Claim 1 wherein the anionically polymerized monomer is polymerized in the presence of an organic dilithium initiator.
4. A block copolymer of ABA configuration in which A represents a random copolymer of styrene and acrylonitrile or a polymer of bromostyrene and B
is a diene elastomer block.
18,312-F
is a diene elastomer block.
18,312-F
5. The block copolymer of Claim 4 characterized in that A is a random copolymer of styrene and acrylonitrile.
6. The block copolymer of Claim 4 characterized in that A is a random copolymer of bromo-styrene.
7. An ABA block copolymer of butadiene and a random copolymer of styrene and acrylonitrile prepared by the process of Claim 1 further characterized in that block B is a homopolymer of butadiene or isoprene having a molecular weight of 30,000 to 500,000 and block A is a random copolymer containing 95 to 50 parts styrene and 5 to 50 parts acrylonitrile by weight and having a weight average molecular weight of 3,000 to 100,000 by gel permeation chromatography.
18,312-F
18,312-F
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78281477A | 1977-03-30 | 1977-03-30 | |
| US782,814 | 1977-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098637A true CA1098637A (en) | 1981-03-31 |
Family
ID=25127248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA298,867A Expired CA1098637A (en) | 1977-03-30 | 1978-03-14 | Preparation of block copolymers and products therefrom |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS53121895A (en) |
| AU (1) | AU521579B2 (en) |
| BE (1) | BE865465A (en) |
| BR (1) | BR7801948A (en) |
| CA (1) | CA1098637A (en) |
| DE (1) | DE2813328C2 (en) |
| FR (1) | FR2385750A1 (en) |
| GB (1) | GB1565042A (en) |
| NL (1) | NL186090C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3611705A1 (en) * | 1986-04-08 | 1987-10-22 | Basf Ag | METHOD FOR PRODUCING IMPACT RESISTANT POLY (ALKYL) STYRENE |
| DE3611704A1 (en) * | 1986-04-08 | 1987-10-22 | Basf Ag | METHOD FOR PRODUCING IMPACT RESISTANT POLY (ALKYL) STYRENE |
| GB2271074B (en) * | 1992-09-24 | 1996-07-10 | Extract Technology Ltd | Glove box |
| CN1795219A (en) * | 2003-05-30 | 2006-06-28 | 日本曹达株式会社 | Process for producing polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3225120A (en) * | 1962-05-16 | 1965-12-21 | Du Pont | Thermoplastic copolymer of vinyl monomer and sulfur |
| SE339105B (en) * | 1966-02-23 | 1971-09-27 | Avisun Corp | |
| GB1234581A (en) * | 1967-09-13 | 1971-06-03 | ||
| FR2071337A5 (en) * | 1969-12-24 | 1971-09-17 | V Trudov | Hydrocarbon polymers having functional - end groups |
| JPS5645923B2 (en) * | 1973-02-12 | 1981-10-29 |
-
1978
- 1978-03-14 CA CA298,867A patent/CA1098637A/en not_active Expired
- 1978-03-22 JP JP3279878A patent/JPS53121895A/en active Granted
- 1978-03-23 NL NL7803192A patent/NL186090C/en not_active IP Right Cessation
- 1978-03-28 DE DE19782813328 patent/DE2813328C2/en not_active Expired
- 1978-03-28 FR FR7808906A patent/FR2385750A1/en active Granted
- 1978-03-29 GB GB1231878A patent/GB1565042A/en not_active Expired
- 1978-03-30 BR BR7801948A patent/BR7801948A/en unknown
- 1978-03-30 BE BE2056814A patent/BE865465A/en not_active IP Right Cessation
- 1978-04-13 AU AU35082/78A patent/AU521579B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL186090B (en) | 1990-04-17 |
| FR2385750A1 (en) | 1978-10-27 |
| BE865465A (en) | 1978-10-02 |
| JPS6229444B2 (en) | 1987-06-26 |
| BR7801948A (en) | 1978-11-28 |
| GB1565042A (en) | 1980-04-16 |
| JPS53121895A (en) | 1978-10-24 |
| DE2813328C2 (en) | 1986-11-27 |
| FR2385750B1 (en) | 1980-02-01 |
| DE2813328A1 (en) | 1978-10-05 |
| NL7803192A (en) | 1978-10-03 |
| AU3508278A (en) | 1979-10-18 |
| NL186090C (en) | 1990-09-17 |
| AU521579B2 (en) | 1982-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3326881A (en) | Polymerization of vinylidene-containing monomers with an initiator consisting of an alkali metal derivative of a functional halogen-substituted aromatic compound | |
| US3078254A (en) | High molecular polymers and method for their preparation | |
| US3251905A (en) | Method of preparing block copolymers of conjugated dienes and vinyl-substituted aromatic compounds using dilithio catalysts and diluent mixture of hydrocarbon and ether | |
| US3598884A (en) | Cross-linking of polymers | |
| US3468972A (en) | Control of branching and coupling in lithium-terminated polymers | |
| US4051199A (en) | Epoxidized copolymers of styrene, butadiene and isoprene | |
| US4169115A (en) | Preparation of block copolymers and products therefrom | |
| US3210333A (en) | Fluidizing polymer solution | |
| US3725505A (en) | Pyrene containing polymers prepared by anionic polymerization | |
| US3322738A (en) | Process for terminating the organolithium catalysis of diene polymerization and produt resulting therefrom | |
| JPS6338379B2 (en) | ||
| US4427837A (en) | Process for preparation of diene-styrene-α-methylstyrene block polymers and polymers therefrom | |
| US3911054A (en) | Process for lowering the viscosity of a solution of a living polymer | |
| US3303225A (en) | Production of polymetallated 1-acetylenes | |
| CA1049189A (en) | Method for producing polystyrene composition | |
| CA1098637A (en) | Preparation of block copolymers and products therefrom | |
| US3755269A (en) | Production of mercaptan-terminated polymers | |
| US3031432A (en) | Process for preparing polystyrene and block copolymers of polystyrene in the presence of an nu-alkyl lithium catalyst | |
| US3159587A (en) | Organopolylithium polymerization initiators and their preparation | |
| US3560593A (en) | Production of block copolymers | |
| KR100191475B1 (en) | Blanched block copolymer, process for its preparation and use therefor | |
| US3198774A (en) | Continuous process for the preparation of block copolymers | |
| US3410836A (en) | Polymerization of conjugated dienes with a dilithium complex of an aromatic ketone | |
| Oppenheimer et al. | The synthesis of blockcopolymers by radical polymerization | |
| Orr et al. | The synthesis and identification of block polymers of butadiene and styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |