CA1077645A - Process for the production of thermoplastically processible rubber - Google Patents
Process for the production of thermoplastically processible rubberInfo
- Publication number
- CA1077645A CA1077645A CA240,986A CA240986A CA1077645A CA 1077645 A CA1077645 A CA 1077645A CA 240986 A CA240986 A CA 240986A CA 1077645 A CA1077645 A CA 1077645A
- Authority
- CA
- Canada
- Prior art keywords
- diblock
- polymers
- styrene
- polymer
- butadiene
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
- C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
Abstract
A PROCESS FOR THE PRODUCTION OF THERMOPLASTICALLY PROCESSIBLE
RUBBER
Abstract of the Disclosure A process for the production of polysegment copolymers with thermoelastomeric properties, wherein block polymers of the idealised form Sx-By, in which S represents structural units de-rived from styrene, B represents structural units derived from a conjugated diene and x and y are integers, is reacted with sul-phur chlorides.
The products obtained in accordance with the invention are suitable for the production of shoe soles, hoses and industrial.
rubber articles.
RUBBER
Abstract of the Disclosure A process for the production of polysegment copolymers with thermoelastomeric properties, wherein block polymers of the idealised form Sx-By, in which S represents structural units de-rived from styrene, B represents structural units derived from a conjugated diene and x and y are integers, is reacted with sul-phur chlorides.
The products obtained in accordance with the invention are suitable for the production of shoe soles, hoses and industrial.
rubber articles.
Description
Linear block polymers of the idealized form S -By~Sz, in which S
represents a structural unit derived from styrene, B represents a structural unit derived from a conjugated diene (butadiene or isoprene) and x, y and z represent integers, are already known. They are used as thermoplastically processible elastomers (Gummi, Asbest, Kunststoffe, 5, 1973, 387).
Block polymers of the idealized form SX-B (the symbols having the same meaning as defined above) are also known. Block polymers of this kind are likewise denoted as "diblock copolymers". Their technological value is only small. They are obtained inter alia by polymerizing styrene and a conjugated diene (butadiene or isoprene) on lithium catalysts in the form of "living polymers", i.e. polymers which, following the addition of further monomers, continue polymerizing in tlle absence of fresh catalyst, unless they have been previously deactivated.
According to DT-AS 1,245,132, "living diblock copolymers", which have been produced in a cértain way, i.e. by polymerizing first s~yrene and then the diene, can be converted by reaction with divinyl benzene into poly-segment polymers of the form SX-By~Cz~By~S (C = polymerized radical of the divinyl benzene). It is rather difficult to carry out this process because insoluble gels are readily formed by cross-linking.
The present invention also provides a polysegment co-polymer con-sisting of coupled diblock co-polymers produced by coupling diblock co-polymers of styrene which is unsubstituted or substituted at the nucleus by halogen or vinyl benzene and unsubstituted or substituted at the side chain by a lower alkyl radical, and a conjugated diene of the idealized form SX-By wherein the styrene block S has 10 - 5000 structural units x and the diene block B has 190 - 19 000 structural units y with 0.5 - 20 mMol of sulphur chlorides per 100 g of diblock co-polymer.
Whereas the known process for the production of - 1 - .~:
polysegment copolymers can only be carried out with "living ~o]ymers", any deactivated diblock copolymers may be used in the process according to the invention. The known process requires an ad~itional diiunctional monomer (divinyl benzene) which is incorporated as an additional block in the polyblock copolymers. No such additional block is formed in the process according to the invention. Accordingly, the products obtained are not only chemically different but they also dif~er in their phrsical properties.
The diblock copolymers used as the starting material for the process according to the invention may be obtained in known manner by anionic, cationic or radical polymerisation.
In the case of anionic polymerisation, for example on lithium alkyl catalysts, styrene and the conjugated diene, preferably butadiene, may be simultaneously subjected to polymerisation. Alternatively~ it is possible to polymerise flrst the styrene and then the diene~ or first the diene and then the styrene.
~Suitable con~ugated dienes are~ in particular~
acyclic dienes containing from 4 to 8 carbon atoms~ for example butadiene~ isoprene and piperylene. Butadiene and i~oprene are preferably used.
In the context of the invention, styrene and structural units derived from styrene also include nucleus-substituted styrenes (ior example vinyl toluene or chloro-styrene) and ~tyrene~ alkylated in the side chain~ ior example a-methyl styrene.
~ he production oi diblock copolymers by anionic polymerisation is known. Polymerisation is preferably carrled out ln hydrocarbons a~ solvents, whilst lithium compounds, Le A 16 162 - 2 -.
1~77645 for example lithium alkyls, are generally used as catalysts. One of the two monomers may be polymerised first and the second added on completion of polymerisation. However, it is also possible to introduce both monomers simultaneously. In this case, the diene polymerises ~irst and ~orms a polydiene block which only contains small quantities of styrene. After the diene has been used up the styrene polymerises and ~orms a polystyrene block which contains practically no diene. The steric structure of the polydiene block may be influenced by cocatalysts, such as for example ethers or amines.
This procedure results initially in the iormation of a living polymer which is deactivated by the addition of ~roton-active agents, such as water, ethyl alcohol, acids or amines. The diblock copolymer thus obtained may be isolated and sub~equently æubjected to the process according to the invention. Alternatively, the deactivated solution obtained may be directly treated with the sulphur chlorides. It i9 ; also possible not to deactivate the dib]ock polymer and insteaA to treat the reaction solution directly with the sulphur chloricles. In thi~ case~ at least the same molar quantity of fiulphur ohlorlde, based on the lithium, iB used.
Disulphur dichloride i8 preferably used as the sulphur chloride The dlblock polymers used pre~erably contaln styrene and/or a-methyl styrene as the hard component with a glass transition temperature above 10C. The soft component (glass transition temperature below 0C) ie preferably iormed by diene rubbers, such as butadiene or lsoprene. The diene component is predominantly present in ~0 the iorm of 1,4-bonds. However, it may also contain ~ I
Le A_16 162 _ ~ _ ~al77~;45 up to 8Q% of 1,2-bonds.
The molecular weight of the styrene block may be between 1000 and 500,000, preferably between 5000 and 100,000 whilst the molecular weight of the rubber block should be between 10,000 and 1,000,000 and preferably between 20,000 and 500,000.
The reaction of sulphur chlorides with diene polymers is known.
It is used to improve "cold flow", especially in the production of cis-l, 4-polybutadiene, the other properties of the rubber remaining unaffected.
(British patent 1,118,615 issued July 3, 1968 to Nutzel et al assigned to the applicant herein.) Surprisingly, it has now been found that the reaction of diblOckco-polymer5 of styrene and butadiene, which have hardly any technological value, with sulphur chlorides results in the formation of polymers which can be processed by processes of the kind normally used for thermoplasts and which at the same time show elastomeric properties.
The products obtained in accordance with the invention are thermoplastic and may be processed in the absence of additives in injection-moulding machines, extruders or the like. At room temperature they show typical rubber properties, i.e. a high modulus, high elongation, hardness and elasticity. Whereas triblock co-polymersof dienes and styrene have the serious disadvantage of undergoing a drastic deterioration in hardness, elasticity and moduli at elevated temperature, these values are reduced to a very much lesser extent in the polymers produced in accordance with the invention.
The products obtained by coupling with the sulphur chlorides are characteristerised by predominant bonding of-the diene components of two or more diblock molecules of the structure S -By. Triblocks S -Bz-S are :~
formed in ~' .
.. .
the first stage, their middle block Bz being formed from the two blocks By o~ the starting components by bonding through sulphur bridges. Bz is branched with a high degree of probability.
The cross-linking does not stop after the reaction between two molecules. As can be shown by gel permeation chromatography, a very wide distribution spectrum is formed. In the accompanying drawing (a gel permeation chromatogram), the abscissa represents the elution volume and the ordinate represents the relative con-centration. I = dib~ock butadiene/styrene, II = I coupled with disulphur dichloride). This wide distribution is responsible for the excellent processing properties of the products obtained.
It is sur~rising that the products obtained show excellent solubilities in h~d rocarbon solvents. They are soluble even in chloroform and9 in some cases, even in ethyl acetate, The high solubility, even of extremely high molecular weight fractions, in aromatic solvents and chloroform, indicates a more spherical structure of the molecules. ~his ls also indicated by the low vis008ity number of the products.
I'his structure distinguishes the polymers produced in accordance with the invention both from triblock copolymer 9 of the type SBS a3 well as from polymers produced by reacting living diblock copolymers with divinyl benzene.
Solvents suitable for use in the proces~ according to the invention include any solvent in which the diblock copolymers are soluble. It is preferred to use the solvents in which the diblock polymers are formed, for example aliphatic hydrocarbons, cyclic hydrocarbons, aromatic solvents or mixturec thereof with ethers or cyclic ethers~ If the diblock polymers Le A 16 162 - 5 -.
~077645 have been isolated in the form of solids by any given proces~, it is also possible to use other solvents for the coupling reaction providing they do not react with or result in the decomposition of the sulphur chlorides~
The sulphur chlorides are preferably added in the form of A solution in the same solvent as that of the diblock.
They may also be added in un~iluted form as liquids.
The re~ction temperatures may be in the range Or irom -20 to ~150C, although the reaction is preferably carried out at room temperature The reaction time ranges from 5 to 120 minutes9 preferably from 15 to 60 minutes~
depending upon the reaction temperature.
The quantity in which the crosslinking agent i8 used depends on the required degree o~ cross-linking. The crosslinking agent may be used,for example, in quantities of from 0.5 to 20 m~lol and preferably in quantities of from 3 to 6 mMol per 100 g o~ rubber.
The process may also be carried out in the absence of ~olvents, In this case~ the ~ulphur chloride~ are elther previouely added in solution to the diblock copolymer and the mixture subsequently isolated by the usual methods~ or they are added in concentrated form or in the form of a concentrated solution in a mixer. Suitable mixers are~ for example~ two-roll or multi-roll stands~ internal mlxers or screw extruder~3.
The process may be carried out either oontinuously or in batches. In lts continuous i~orm, the reaction may be carrled out in reactor cascadea or in tube reactora.
The polymer i9 recovered from its solution either by precipitation with an organic non-~olvent or by coagulation 3o with hot water. A ~tabiliser may be added to the polymer ~ - 6 -~7764S
before this stage.
The products obtained in accordance with the invention are suitable for the production of shoe soles, hoses and industrial rubber articles.
The polymers may be processed in the absence of additives~
although it is also possible to add conventional rubber additives, such as carbon black, light fillers, dyes, pigments or processing oils.
In the following examples the percentages are by weight.
Le A 16 162 - 7 _ :
1~77645 Example 1 22.4 litres of dry toluene are initially introduced into a 60 litre vessel in the absence of air and moisture.
3.12 kg of dry styrene are added and polymerisation is initiate~ by the addition of 31.2 mol of 2M n-butyl lithium.
The t~m~erature is kept between 30 and 50C. After 3 hours, 3.12 kg of butadiene are added and the mixture is left to ~olymerise for 15 hours at the eame temperature. 0.40,h of S2C12 (based on the rubber) dissolved in toluene i9 then added, and the mixture is left to react for 30 minutes at room temperature. The solution is then stabilised by the addition of 0.5B of di-tert-butyl methyl phenol and the rubber is isolated by precipitation with methanol. An almost co]ourless product i8 obtained after drying at 70C
in a vacuum drying cabinet. Sheets produced from this product by pressing for 10 minutes at 170C were tested ln comparison with a ~tandard co~mercial-grade thermopla~tic rubber (trade name ~ariflex TR 4122~.
Produced in Standard accordance with commercial Example 1 product F ~trength (MPa) 6.6 7.2 D elongation (/0) 530 970 M modulus 300 (MPa) 4.1 1.6 M modulus 500 (MPR) 6. 5 2.6 H hardnes~ 20/70a (Shore A) 94/91 71/45 H hardness 100/120/150 42/17/4 7/1/-E elastlclty 20/70 46/39 38/30 Str. structure aocordln~ 94 97 to Pohle (N) It can be seen that the product according to the Le A 16 152 - 8 -.
fr$lp ~
'' ~ - ' .
invention is superior to the stanAard commercial product in numerous aspects, but especially in the modulus values. In addition, the product shows greater hardness, coupled with higher elasticity, than the standard co~mercial product. The dependence upon temperature of hardness is of particular significance. The product according to the invention shows a considerably lower reduction in hardness with increasing temperature. It also shows advantages during extrusion.
Whereas the profile obtained with the standard commercial-grade product was slightly rough and showed signs of injection swelling, the product according to the invention showed a smooth profile without any in;ection swelling.
Example 2 1.1 litres of dry toluene were introduced into a
represents a structural unit derived from styrene, B represents a structural unit derived from a conjugated diene (butadiene or isoprene) and x, y and z represent integers, are already known. They are used as thermoplastically processible elastomers (Gummi, Asbest, Kunststoffe, 5, 1973, 387).
Block polymers of the idealized form SX-B (the symbols having the same meaning as defined above) are also known. Block polymers of this kind are likewise denoted as "diblock copolymers". Their technological value is only small. They are obtained inter alia by polymerizing styrene and a conjugated diene (butadiene or isoprene) on lithium catalysts in the form of "living polymers", i.e. polymers which, following the addition of further monomers, continue polymerizing in tlle absence of fresh catalyst, unless they have been previously deactivated.
According to DT-AS 1,245,132, "living diblock copolymers", which have been produced in a cértain way, i.e. by polymerizing first s~yrene and then the diene, can be converted by reaction with divinyl benzene into poly-segment polymers of the form SX-By~Cz~By~S (C = polymerized radical of the divinyl benzene). It is rather difficult to carry out this process because insoluble gels are readily formed by cross-linking.
The present invention also provides a polysegment co-polymer con-sisting of coupled diblock co-polymers produced by coupling diblock co-polymers of styrene which is unsubstituted or substituted at the nucleus by halogen or vinyl benzene and unsubstituted or substituted at the side chain by a lower alkyl radical, and a conjugated diene of the idealized form SX-By wherein the styrene block S has 10 - 5000 structural units x and the diene block B has 190 - 19 000 structural units y with 0.5 - 20 mMol of sulphur chlorides per 100 g of diblock co-polymer.
Whereas the known process for the production of - 1 - .~:
polysegment copolymers can only be carried out with "living ~o]ymers", any deactivated diblock copolymers may be used in the process according to the invention. The known process requires an ad~itional diiunctional monomer (divinyl benzene) which is incorporated as an additional block in the polyblock copolymers. No such additional block is formed in the process according to the invention. Accordingly, the products obtained are not only chemically different but they also dif~er in their phrsical properties.
The diblock copolymers used as the starting material for the process according to the invention may be obtained in known manner by anionic, cationic or radical polymerisation.
In the case of anionic polymerisation, for example on lithium alkyl catalysts, styrene and the conjugated diene, preferably butadiene, may be simultaneously subjected to polymerisation. Alternatively~ it is possible to polymerise flrst the styrene and then the diene~ or first the diene and then the styrene.
~Suitable con~ugated dienes are~ in particular~
acyclic dienes containing from 4 to 8 carbon atoms~ for example butadiene~ isoprene and piperylene. Butadiene and i~oprene are preferably used.
In the context of the invention, styrene and structural units derived from styrene also include nucleus-substituted styrenes (ior example vinyl toluene or chloro-styrene) and ~tyrene~ alkylated in the side chain~ ior example a-methyl styrene.
~ he production oi diblock copolymers by anionic polymerisation is known. Polymerisation is preferably carrled out ln hydrocarbons a~ solvents, whilst lithium compounds, Le A 16 162 - 2 -.
1~77645 for example lithium alkyls, are generally used as catalysts. One of the two monomers may be polymerised first and the second added on completion of polymerisation. However, it is also possible to introduce both monomers simultaneously. In this case, the diene polymerises ~irst and ~orms a polydiene block which only contains small quantities of styrene. After the diene has been used up the styrene polymerises and ~orms a polystyrene block which contains practically no diene. The steric structure of the polydiene block may be influenced by cocatalysts, such as for example ethers or amines.
This procedure results initially in the iormation of a living polymer which is deactivated by the addition of ~roton-active agents, such as water, ethyl alcohol, acids or amines. The diblock copolymer thus obtained may be isolated and sub~equently æubjected to the process according to the invention. Alternatively, the deactivated solution obtained may be directly treated with the sulphur chlorides. It i9 ; also possible not to deactivate the dib]ock polymer and insteaA to treat the reaction solution directly with the sulphur chloricles. In thi~ case~ at least the same molar quantity of fiulphur ohlorlde, based on the lithium, iB used.
Disulphur dichloride i8 preferably used as the sulphur chloride The dlblock polymers used pre~erably contaln styrene and/or a-methyl styrene as the hard component with a glass transition temperature above 10C. The soft component (glass transition temperature below 0C) ie preferably iormed by diene rubbers, such as butadiene or lsoprene. The diene component is predominantly present in ~0 the iorm of 1,4-bonds. However, it may also contain ~ I
Le A_16 162 _ ~ _ ~al77~;45 up to 8Q% of 1,2-bonds.
The molecular weight of the styrene block may be between 1000 and 500,000, preferably between 5000 and 100,000 whilst the molecular weight of the rubber block should be between 10,000 and 1,000,000 and preferably between 20,000 and 500,000.
The reaction of sulphur chlorides with diene polymers is known.
It is used to improve "cold flow", especially in the production of cis-l, 4-polybutadiene, the other properties of the rubber remaining unaffected.
(British patent 1,118,615 issued July 3, 1968 to Nutzel et al assigned to the applicant herein.) Surprisingly, it has now been found that the reaction of diblOckco-polymer5 of styrene and butadiene, which have hardly any technological value, with sulphur chlorides results in the formation of polymers which can be processed by processes of the kind normally used for thermoplasts and which at the same time show elastomeric properties.
The products obtained in accordance with the invention are thermoplastic and may be processed in the absence of additives in injection-moulding machines, extruders or the like. At room temperature they show typical rubber properties, i.e. a high modulus, high elongation, hardness and elasticity. Whereas triblock co-polymersof dienes and styrene have the serious disadvantage of undergoing a drastic deterioration in hardness, elasticity and moduli at elevated temperature, these values are reduced to a very much lesser extent in the polymers produced in accordance with the invention.
The products obtained by coupling with the sulphur chlorides are characteristerised by predominant bonding of-the diene components of two or more diblock molecules of the structure S -By. Triblocks S -Bz-S are :~
formed in ~' .
.. .
the first stage, their middle block Bz being formed from the two blocks By o~ the starting components by bonding through sulphur bridges. Bz is branched with a high degree of probability.
The cross-linking does not stop after the reaction between two molecules. As can be shown by gel permeation chromatography, a very wide distribution spectrum is formed. In the accompanying drawing (a gel permeation chromatogram), the abscissa represents the elution volume and the ordinate represents the relative con-centration. I = dib~ock butadiene/styrene, II = I coupled with disulphur dichloride). This wide distribution is responsible for the excellent processing properties of the products obtained.
It is sur~rising that the products obtained show excellent solubilities in h~d rocarbon solvents. They are soluble even in chloroform and9 in some cases, even in ethyl acetate, The high solubility, even of extremely high molecular weight fractions, in aromatic solvents and chloroform, indicates a more spherical structure of the molecules. ~his ls also indicated by the low vis008ity number of the products.
I'his structure distinguishes the polymers produced in accordance with the invention both from triblock copolymer 9 of the type SBS a3 well as from polymers produced by reacting living diblock copolymers with divinyl benzene.
Solvents suitable for use in the proces~ according to the invention include any solvent in which the diblock copolymers are soluble. It is preferred to use the solvents in which the diblock polymers are formed, for example aliphatic hydrocarbons, cyclic hydrocarbons, aromatic solvents or mixturec thereof with ethers or cyclic ethers~ If the diblock polymers Le A 16 162 - 5 -.
~077645 have been isolated in the form of solids by any given proces~, it is also possible to use other solvents for the coupling reaction providing they do not react with or result in the decomposition of the sulphur chlorides~
The sulphur chlorides are preferably added in the form of A solution in the same solvent as that of the diblock.
They may also be added in un~iluted form as liquids.
The re~ction temperatures may be in the range Or irom -20 to ~150C, although the reaction is preferably carried out at room temperature The reaction time ranges from 5 to 120 minutes9 preferably from 15 to 60 minutes~
depending upon the reaction temperature.
The quantity in which the crosslinking agent i8 used depends on the required degree o~ cross-linking. The crosslinking agent may be used,for example, in quantities of from 0.5 to 20 m~lol and preferably in quantities of from 3 to 6 mMol per 100 g o~ rubber.
The process may also be carried out in the absence of ~olvents, In this case~ the ~ulphur chloride~ are elther previouely added in solution to the diblock copolymer and the mixture subsequently isolated by the usual methods~ or they are added in concentrated form or in the form of a concentrated solution in a mixer. Suitable mixers are~ for example~ two-roll or multi-roll stands~ internal mlxers or screw extruder~3.
The process may be carried out either oontinuously or in batches. In lts continuous i~orm, the reaction may be carrled out in reactor cascadea or in tube reactora.
The polymer i9 recovered from its solution either by precipitation with an organic non-~olvent or by coagulation 3o with hot water. A ~tabiliser may be added to the polymer ~ - 6 -~7764S
before this stage.
The products obtained in accordance with the invention are suitable for the production of shoe soles, hoses and industrial rubber articles.
The polymers may be processed in the absence of additives~
although it is also possible to add conventional rubber additives, such as carbon black, light fillers, dyes, pigments or processing oils.
In the following examples the percentages are by weight.
Le A 16 162 - 7 _ :
1~77645 Example 1 22.4 litres of dry toluene are initially introduced into a 60 litre vessel in the absence of air and moisture.
3.12 kg of dry styrene are added and polymerisation is initiate~ by the addition of 31.2 mol of 2M n-butyl lithium.
The t~m~erature is kept between 30 and 50C. After 3 hours, 3.12 kg of butadiene are added and the mixture is left to ~olymerise for 15 hours at the eame temperature. 0.40,h of S2C12 (based on the rubber) dissolved in toluene i9 then added, and the mixture is left to react for 30 minutes at room temperature. The solution is then stabilised by the addition of 0.5B of di-tert-butyl methyl phenol and the rubber is isolated by precipitation with methanol. An almost co]ourless product i8 obtained after drying at 70C
in a vacuum drying cabinet. Sheets produced from this product by pressing for 10 minutes at 170C were tested ln comparison with a ~tandard co~mercial-grade thermopla~tic rubber (trade name ~ariflex TR 4122~.
Produced in Standard accordance with commercial Example 1 product F ~trength (MPa) 6.6 7.2 D elongation (/0) 530 970 M modulus 300 (MPa) 4.1 1.6 M modulus 500 (MPR) 6. 5 2.6 H hardnes~ 20/70a (Shore A) 94/91 71/45 H hardness 100/120/150 42/17/4 7/1/-E elastlclty 20/70 46/39 38/30 Str. structure aocordln~ 94 97 to Pohle (N) It can be seen that the product according to the Le A 16 152 - 8 -.
fr$lp ~
'' ~ - ' .
invention is superior to the stanAard commercial product in numerous aspects, but especially in the modulus values. In addition, the product shows greater hardness, coupled with higher elasticity, than the standard co~mercial product. The dependence upon temperature of hardness is of particular significance. The product according to the invention shows a considerably lower reduction in hardness with increasing temperature. It also shows advantages during extrusion.
Whereas the profile obtained with the standard commercial-grade product was slightly rough and showed signs of injection swelling, the product according to the invention showed a smooth profile without any in;ection swelling.
Example 2 1.1 litres of dry toluene were introduced into a
2 litre autoolave in the absence of air and moisture. 192 g of dry butadiene are added and polymerisation is initiated by the addition of 1.3 ml o~ 2 M sec-butyl lithium. The temperature is kept at 40 to 60C. After 3 hours, 127 g of styrene are added, and the mixture is left to polymerise for another 3 hours.
The llving polymer is deactivated by the addition of 0.32 g of 2~6-di-tert-butyl-4-methyl phenol in toluene.
0.4G/o of S2C12 is then added, based on solid rubber~ and the mixture ls left reacting ior 60 minutes~ Aiter isolatlon by coagulation with steam, the product i9 drled at 70C
in a vacuum drying cabinet. Sheets pressed ~rom the polymer (10 minutes~ 170C) show the following properties:
F 6.9 MPa~ D 4755~ M 300 /0 4.2 MPa, H (23~ 70, 100, 120~ 150) 83, 70~ 52, 30~ 12; E 23/70 47/38~ Str 100~
, abrasion (40/60 emery) 135/68 mm3. T~e standard commercial
The llving polymer is deactivated by the addition of 0.32 g of 2~6-di-tert-butyl-4-methyl phenol in toluene.
0.4G/o of S2C12 is then added, based on solid rubber~ and the mixture ls left reacting ior 60 minutes~ Aiter isolatlon by coagulation with steam, the product i9 drled at 70C
in a vacuum drying cabinet. Sheets pressed ~rom the polymer (10 minutes~ 170C) show the following properties:
F 6.9 MPa~ D 4755~ M 300 /0 4.2 MPa, H (23~ 70, 100, 120~ 150) 83, 70~ 52, 30~ 12; E 23/70 47/38~ Str 100~
, abrasion (40/60 emery) 135/68 mm3. T~e standard commercial
3 A comparison material (Cariflex TR 4122~ showed the iollowing Le A 16 162 - 9 -7~r~
- ... . ~ . . . : .
.
. . . . . . . . . . .
values: ~ 6.~ MPa, 1) 99S', M (300%) 3.5 MPa, H(23, 70, 100, 1~(), ]50) 76, 51, 6, 1, 0; ~(23/70) 40/41, Str. 88, a~ra~sion (40/~ emery) 277/170.
I~`xamT)l e ].1 litres of dry toluene are introduced into a 2 ~itre autoclave in the absence o~ air and moisture. 91 g of drv styrene are added and the polymerisation reaction is initiated by the addition of 3.6 ml of 2 M n-butyl lithium.
~fter 3 hours at 30-40C, dry isoprene (260 g) is added and 11o]ymeri~ation continued at 40 to 60C. After 3 hours, o.5~b of 2,h-di-tert-butyl-4-methyl phenol (based on rubber) is added and the product is precipitated with methanol (~) = 0.72 dl/g. After drying, the polymer is dissolved in toluene and freed from traces of moisture by introducing nitrogen at 70C. After cooling to room temperature~ 1.0 of disulphur dichloride ~based on rubber) is added~ followed by stirring for 60 minutes. The product is isolated in the same way as described above, an elastic, somewhat tacky polymer being obtained. It ha~ an (~)-value of 1.59 dl/g.
Exam~le 4 A somewhat tacky polymer is obtained ln the same way as de~cribed ln Example 3, except that a mlxture of 195 g of butadiene and 65 g of isoprene ls used. Before treatment wlth 1 phr of S2C12~ the polymer has an (~)-value $ 0.61. After the reaction, it~ value i3 0.~7.
Le A 16 162 - 10 -
- ... . ~ . . . : .
.
. . . . . . . . . . .
values: ~ 6.~ MPa, 1) 99S', M (300%) 3.5 MPa, H(23, 70, 100, 1~(), ]50) 76, 51, 6, 1, 0; ~(23/70) 40/41, Str. 88, a~ra~sion (40/~ emery) 277/170.
I~`xamT)l e ].1 litres of dry toluene are introduced into a 2 ~itre autoclave in the absence o~ air and moisture. 91 g of drv styrene are added and the polymerisation reaction is initiated by the addition of 3.6 ml of 2 M n-butyl lithium.
~fter 3 hours at 30-40C, dry isoprene (260 g) is added and 11o]ymeri~ation continued at 40 to 60C. After 3 hours, o.5~b of 2,h-di-tert-butyl-4-methyl phenol (based on rubber) is added and the product is precipitated with methanol (~) = 0.72 dl/g. After drying, the polymer is dissolved in toluene and freed from traces of moisture by introducing nitrogen at 70C. After cooling to room temperature~ 1.0 of disulphur dichloride ~based on rubber) is added~ followed by stirring for 60 minutes. The product is isolated in the same way as described above, an elastic, somewhat tacky polymer being obtained. It ha~ an (~)-value of 1.59 dl/g.
Exam~le 4 A somewhat tacky polymer is obtained ln the same way as de~cribed ln Example 3, except that a mlxture of 195 g of butadiene and 65 g of isoprene ls used. Before treatment wlth 1 phr of S2C12~ the polymer has an (~)-value $ 0.61. After the reaction, it~ value i3 0.~7.
Le A 16 162 - 10 -
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polysegment co-polymer consisting of coupled diblock co-polymers produced by coupling diblock co-polymers of styrene which is unsubstituted or substituted at the nucleus by halogen or vinyl benzene and unsubstituted or substituted at the side chain by a lower alkyl radical, and a conjugated diene of the idealized form Sx-By wherein the styrene block S has 10 - 5000 structural units x and the diene block B has 190 - 19 000 structural units y with 0.5 - 20 mMol of sulphur chlorides per 100 g of diblock co-polymer.
2. A polysegment co-polymer according to claim 1, comprising diblock co-polymers of styrene and diblock co-polymers of butadiene.
3. A polysegment co-polymer according to claim 2, wherein the diblock co-polymer of butadiene is a diblock co-polymer of 1,3-butadiene.
4. A polysegment co-polymer according to claim 2, wherein the diblock co-polymer of butadiene is a diblock co-polymer formed from a mixture of 20 to 100% 1,3-butadiene and 80 to 0% of 1,2-butadiene.
5. A polysegment co-polymer according to claim 1, comprising diblock co-polymers of styrene and diblock co-polymers of isoprene.
6. A polysegment co-polymer according to claim 1, comprising diblock co-polymers of styrene and diblock co-polymers of an acyclic diene of from 4 to 8 carbon atoms.
7. A polysegment co-polymer according to claim 1, comprising diblock co-polymers of styrene and diblock co-polymers of piperylene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2457388A DE2457388C2 (en) | 1974-12-05 | 1974-12-05 | Thermoelastomeric poly-segment copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077645A true CA1077645A (en) | 1980-05-13 |
Family
ID=5932498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,986A Expired CA1077645A (en) | 1974-12-05 | 1975-12-03 | Process for the production of thermoplastically processible rubber |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5182388A (en) |
| BE (1) | BE836273A (en) |
| BR (1) | BR7508041A (en) |
| CA (1) | CA1077645A (en) |
| DE (1) | DE2457388C2 (en) |
| ES (1) | ES443195A1 (en) |
| FR (1) | FR2293447A1 (en) |
| GB (1) | GB1512557A (en) |
| IT (1) | IT1052486B (en) |
| NL (1) | NL7514026A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6579940B1 (en) | 1999-10-28 | 2003-06-17 | Edwards Lifesciences Corporation | Thermoplastic elastomeric material as a replacement for natural rubber latex |
| DE10003743A1 (en) * | 2000-01-28 | 2001-08-16 | Bayer Ag | Process for the preparation of a copolymer based on vinyl aromatic compounds and conjugated dienes |
| ES2606834T3 (en) * | 2013-12-20 | 2017-03-28 | Continental Reifen Deutschland Gmbh | Mixture of rubber and car tires |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3374191A (en) * | 1965-08-05 | 1968-03-19 | Bayer Ag | Process for the production of elastomeric diene polymers with improved properties |
| DE1570099B2 (en) * | 1965-05-26 | 1976-07-15 | Bayer Ag, 5090 Leverkusen | PROCESS FOR MANUFACTURING OIL-EXTENDED UNSATURATED ELASTOMERIZED POLYMERIZES |
| US3607979A (en) * | 1968-10-24 | 1971-09-21 | Shell Oil Co | Hydrophilic chlorosulfonated block copolymers |
| US3694521A (en) * | 1970-07-31 | 1972-09-26 | Shell Oil Co | Chlorosulfonated block copolymers |
| DE2533947A1 (en) * | 1975-07-30 | 1977-02-17 | Hoechst Ag | METAL-CONTAINING DISAZOMETHINE COMPOUNDS, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS A COLORANT |
-
1974
- 1974-12-05 DE DE2457388A patent/DE2457388C2/en not_active Expired
-
1975
- 1975-10-29 GB GB44589/75A patent/GB1512557A/en not_active Expired
- 1975-12-02 NL NL7514026A patent/NL7514026A/en unknown
- 1975-12-03 JP JP50143043A patent/JPS5182388A/ja active Pending
- 1975-12-03 CA CA240,986A patent/CA1077645A/en not_active Expired
- 1975-12-03 IT IT52505/75A patent/IT1052486B/en active
- 1975-12-04 BR BR7508041*A patent/BR7508041A/en unknown
- 1975-12-04 ES ES443195A patent/ES443195A1/en not_active Expired
- 1975-12-04 BE BE162445A patent/BE836273A/en not_active IP Right Cessation
- 1975-12-05 FR FR7537334A patent/FR2293447A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7514026A (en) | 1976-06-09 |
| DE2457388C2 (en) | 1982-12-02 |
| FR2293447B1 (en) | 1979-07-20 |
| FR2293447A1 (en) | 1976-07-02 |
| JPS5182388A (en) | 1976-07-19 |
| ES443195A1 (en) | 1977-04-16 |
| BR7508041A (en) | 1976-08-24 |
| BE836273A (en) | 1976-06-04 |
| DE2457388A1 (en) | 1976-06-10 |
| IT1052486B (en) | 1981-06-20 |
| GB1512557A (en) | 1978-06-01 |
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