CA1222345A - Vulcanizable compounds - Google Patents
Vulcanizable compoundsInfo
- Publication number
- CA1222345A CA1222345A CA000428996A CA428996A CA1222345A CA 1222345 A CA1222345 A CA 1222345A CA 000428996 A CA000428996 A CA 000428996A CA 428996 A CA428996 A CA 428996A CA 1222345 A CA1222345 A CA 1222345A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- isoprene
- polymerization
- styrene
- polyisoprene
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Sealing Material Composition (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The application relates to vulcanizable compounds con-taining new rubbers which are special polyisoprenes and amorphous isoprene/styrene copolymers. The compounds, and vulcanized pro-duets produced therefrom, possess an advantageous combination of properties. Worthy of emphasis is the satisfactory covulcanizing ability of the new rubbers when blended with other rubbers the extraordinarily high gastightness of the vulcanized products and, above all, their unusually high resistance to swelling in non-polar organic media.
The application relates to vulcanizable compounds con-taining new rubbers which are special polyisoprenes and amorphous isoprene/styrene copolymers. The compounds, and vulcanized pro-duets produced therefrom, possess an advantageous combination of properties. Worthy of emphasis is the satisfactory covulcanizing ability of the new rubbers when blended with other rubbers the extraordinarily high gastightness of the vulcanized products and, above all, their unusually high resistance to swelling in non-polar organic media.
Description
~3443-261 It is known to use vulcanizablecompounds containing nitrile rubber for producing materials or s-tructural elements for sealing against non-polar organic media, mainly against aliphatic hydrocarbons, for example fuels and mineral oils.
Copolymers of 1,3-butadiene and acrylonitrile are known as nitrile rubber (nitrile butadiene rubber, NBR). Vulcanized pro-ducts made from nitrile rubber are noted for high resistance (resistance to swelling) to non-polar organic media, and are used for elastic seals, tank-hoses, cable-casings and the like. In many cases, however, they are not sufficiently impermeable to gases~
i.e. mainly components of the atmosphere.
Based upon the state of the art outlined above, it is a purpose of the inven-tion to make available vulcanizable compounds which are suitable for the production of materials and structural elements, especially resilient seals, for sealing against non-polar organic media, and which surpass existing vulcanizable com-pounds as a result of an advantageous combination of properties.
This combination of properties includes satisfactory processability during mixing and shaping operations; satisfactory vulcanizing behaviourapproaching that of known, rapidly-reacting all-purpose rubbers (NR, IR, BR and SBR) from the point of view of cross-]inking speed and yield; satisfactory covulcanizing behaviour when blended with all-purpose rubbers, NBR and also EPDM and IIR
(IIR meaning butyl-rubber and chlorina-ted and brominated butyl-rubber which are known as chlorobutyl- and bromobutyl-rubber), and satisfactory covulcanizing behaviour during the production of multi-layer composite materials; the vulcanized products are to be adequately gastight and, above all, adequately resistant to , ~ , 7474/1~ - Zu - 1 - `~
O.Z. 3813/3874 31 2;~2~
swelling in non-polar organic media.
The present invention provides a vulcanizable compound comprising: more than 30 to 100 parts by weight o:E a rubber selected EroM the group of polyisoprenes, amorphous isoprene/sty-rene copolymers and mixtures -thereof having a Mooney viscosity (MLl+4, 100C DIN 53 523) of 30 to 1.20, a Defo elasticity (80~C, DIN 53 51.4) of 12 to 45, a non-homogeneity (U = Mn - 1) of 0.8 to 5.5, and a glass transition temperature (Tg, torsional vibration, damping maximum, DIN 53 520) between -35 and 0C; 0 to less than 70 parts by weight of another rubber of a mixture of other rubbers per 100 parts by weight of rubber, an effec-tive amount of a vulcanizing agent, wherein the polyisoprene is obtained by homopolymerization of isop:rene or by polymerization o:E a monomer mixture of 55 to less than 100% by weight of isoprene, 0 -to 20%
by weight of piperylene, 0 to 45% by weight of 1,3-butadiene, and 0 to less than 1% by weight of styrene in relation to the mGnomer mixture, the said polyisoprene containing an average of between 60 and 85% by weight of structural units obtained by l.,2- and 3,4-polymerization of the dienes; or the isoprene-styrene copolymer is obtained by polymerizatlon of a monomer mixture of 35 to 99%
by weight of isoprene, 1 to 30% by weight of styrene, 0 to 25% by weight of piperylene, and 0 tc- less than 50% by weight of 1,3-butadiene in relation to the monomer mixture, and having an average content of 55 to 90% by weight of structural units obtained by 1,2-and 3,4-polymerization of the dienes and statistical copo.Lymeriza-tion of styrene, the polymerization of the said polyisoprene or isoprene/styrene copolymer being characterized by the following conditions: polymerization in an inert organic solvent in the
Copolymers of 1,3-butadiene and acrylonitrile are known as nitrile rubber (nitrile butadiene rubber, NBR). Vulcanized pro-ducts made from nitrile rubber are noted for high resistance (resistance to swelling) to non-polar organic media, and are used for elastic seals, tank-hoses, cable-casings and the like. In many cases, however, they are not sufficiently impermeable to gases~
i.e. mainly components of the atmosphere.
Based upon the state of the art outlined above, it is a purpose of the inven-tion to make available vulcanizable compounds which are suitable for the production of materials and structural elements, especially resilient seals, for sealing against non-polar organic media, and which surpass existing vulcanizable com-pounds as a result of an advantageous combination of properties.
This combination of properties includes satisfactory processability during mixing and shaping operations; satisfactory vulcanizing behaviourapproaching that of known, rapidly-reacting all-purpose rubbers (NR, IR, BR and SBR) from the point of view of cross-]inking speed and yield; satisfactory covulcanizing behaviour when blended with all-purpose rubbers, NBR and also EPDM and IIR
(IIR meaning butyl-rubber and chlorina-ted and brominated butyl-rubber which are known as chlorobutyl- and bromobutyl-rubber), and satisfactory covulcanizing behaviour during the production of multi-layer composite materials; the vulcanized products are to be adequately gastight and, above all, adequately resistant to , ~ , 7474/1~ - Zu - 1 - `~
O.Z. 3813/3874 31 2;~2~
swelling in non-polar organic media.
The present invention provides a vulcanizable compound comprising: more than 30 to 100 parts by weight o:E a rubber selected EroM the group of polyisoprenes, amorphous isoprene/sty-rene copolymers and mixtures -thereof having a Mooney viscosity (MLl+4, 100C DIN 53 523) of 30 to 1.20, a Defo elasticity (80~C, DIN 53 51.4) of 12 to 45, a non-homogeneity (U = Mn - 1) of 0.8 to 5.5, and a glass transition temperature (Tg, torsional vibration, damping maximum, DIN 53 520) between -35 and 0C; 0 to less than 70 parts by weight of another rubber of a mixture of other rubbers per 100 parts by weight of rubber, an effec-tive amount of a vulcanizing agent, wherein the polyisoprene is obtained by homopolymerization of isop:rene or by polymerization o:E a monomer mixture of 55 to less than 100% by weight of isoprene, 0 -to 20%
by weight of piperylene, 0 to 45% by weight of 1,3-butadiene, and 0 to less than 1% by weight of styrene in relation to the mGnomer mixture, the said polyisoprene containing an average of between 60 and 85% by weight of structural units obtained by l.,2- and 3,4-polymerization of the dienes; or the isoprene-styrene copolymer is obtained by polymerizatlon of a monomer mixture of 35 to 99%
by weight of isoprene, 1 to 30% by weight of styrene, 0 to 25% by weight of piperylene, and 0 tc- less than 50% by weight of 1,3-butadiene in relation to the monomer mixture, and having an average content of 55 to 90% by weight of structural units obtained by 1,2-and 3,4-polymerization of the dienes and statistical copo.Lymeriza-tion of styrene, the polymerization of the said polyisoprene or isoprene/styrene copolymer being characterized by the following conditions: polymerization in an inert organic solvent in the
- 2 -~ 2~
presence of a catalyst system consisting of an amount effective for polymeriza-tion of 0.008 to 0.1% by weigh-t of an organolithium catalyst and 0.1 to 10% by weight of a cocatalyst selected from the group of ethers, tert:iary amines and mixtures -thereof, the weight ratio of cocatalyst:catalyst being between 2:1 and 1,000:1, and in the presence of 0 to 0.1% by weight of divinyl-benzene, related respectively to the monomer, and the polymerization of the polyisoprene or the isoprene/styrene copolymer is carried out at an increasing tempera-ture, starting at between 15 and 50C and :Einishing at 70 -to 145C, the difference between the finishing and starting temperatures being between 40 and 125C.
The vulcanizable compound can also contain the usual additives.
Preferably the polyisoprene or isoprene/s-tyrene copoly-mer possesses a Mooney viscosity of 40 to 100, a Defo elasticity of 20 to 40, a non-homogeneity of 1 to 4, and a glass -transition temperature between -30 and -5C.
~ preferred polyisoprene is obtained by polymerization of a monomer mixture consisting of 65 to 90% by weight of isoprene, 0 to 10% by weight of piperylene, 0 to 35% by weight of 1,3-buta-diene, and 0 to less than 1% by weight of styrene, in relation to the monomer mixture, and has an average content of 65 to 80% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes. A preferred isoprene/styrene copolymer is obtained by polymerization of a monomer mixture consisting of 40 to 90% by weight of isoprene, 10 to 25% by weight of styrene, 0 to 15% by weight of piperylene, and 0 to 40% by weight of 1,3-butadiene, in relation to the monomer mixture, with an average content of 60 to
presence of a catalyst system consisting of an amount effective for polymeriza-tion of 0.008 to 0.1% by weigh-t of an organolithium catalyst and 0.1 to 10% by weight of a cocatalyst selected from the group of ethers, tert:iary amines and mixtures -thereof, the weight ratio of cocatalyst:catalyst being between 2:1 and 1,000:1, and in the presence of 0 to 0.1% by weight of divinyl-benzene, related respectively to the monomer, and the polymerization of the polyisoprene or the isoprene/styrene copolymer is carried out at an increasing tempera-ture, starting at between 15 and 50C and :Einishing at 70 -to 145C, the difference between the finishing and starting temperatures being between 40 and 125C.
The vulcanizable compound can also contain the usual additives.
Preferably the polyisoprene or isoprene/s-tyrene copoly-mer possesses a Mooney viscosity of 40 to 100, a Defo elasticity of 20 to 40, a non-homogeneity of 1 to 4, and a glass -transition temperature between -30 and -5C.
~ preferred polyisoprene is obtained by polymerization of a monomer mixture consisting of 65 to 90% by weight of isoprene, 0 to 10% by weight of piperylene, 0 to 35% by weight of 1,3-buta-diene, and 0 to less than 1% by weight of styrene, in relation to the monomer mixture, and has an average content of 65 to 80% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes. A preferred isoprene/styrene copolymer is obtained by polymerization of a monomer mixture consisting of 40 to 90% by weight of isoprene, 10 to 25% by weight of styrene, 0 to 15% by weight of piperylene, and 0 to 40% by weight of 1,3-butadiene, in relation to the monomer mixture, with an average content of 60 to
- 3 -J4a g~:~f~
85% by weight of structural units obtained by 1,2 and 3,4-polymer-lzation of the dienes and by statistical copolymerization of s-tyrene.
The polyisoprene or the isoprene/styrene copolymer may exhibit a statistical distribution of the structural units corres-ponding to the different monomers. Such copolymers are obtained by polymerization of only one mixture of monomers the composition of which is characterized by the amounts specified above. Under preferxed conditions the difference between the finishing and starting temperatures for the polymerization is between 70 and 120C and the polymerization is terminated at a temperature between 85 and 145C. Alternatively the polyisoprene or the isoprene/
styrene copolymer may exhibit block structures, although blocks of homopolymerized styrene should not be present. The blocks are characterized in that the chain segments, which join a block bound-ary from both sides, differ from each other in the kind or in the number of the basic monomers. All of the monomers of a block polymer taken together have to correspond to the amounts ofthe monomers specified above. Of course these amounts do not neces-sarily apply -to a monomer mixture which is polymerized to yield a block of the block copolymer. If a block structure is required, the polymerization of the isoprene should take place in the lower portion of the temperature range and -the polymeriza-tion of 1,3-butadiene should take place in the upper portion of the tempera-ture range. Preferably such block polymers are obtained by first poly~
merizing isoprene or a monomer mixture containing isoprene up to a conversion of 50 to 90% of the isoprene and then continuing polymerization while adding 1,3~butadiene or a monomer mixture
85% by weight of structural units obtained by 1,2 and 3,4-polymer-lzation of the dienes and by statistical copolymerization of s-tyrene.
The polyisoprene or the isoprene/styrene copolymer may exhibit a statistical distribution of the structural units corres-ponding to the different monomers. Such copolymers are obtained by polymerization of only one mixture of monomers the composition of which is characterized by the amounts specified above. Under preferxed conditions the difference between the finishing and starting temperatures for the polymerization is between 70 and 120C and the polymerization is terminated at a temperature between 85 and 145C. Alternatively the polyisoprene or the isoprene/
styrene copolymer may exhibit block structures, although blocks of homopolymerized styrene should not be present. The blocks are characterized in that the chain segments, which join a block bound-ary from both sides, differ from each other in the kind or in the number of the basic monomers. All of the monomers of a block polymer taken together have to correspond to the amounts ofthe monomers specified above. Of course these amounts do not neces-sarily apply -to a monomer mixture which is polymerized to yield a block of the block copolymer. If a block structure is required, the polymerization of the isoprene should take place in the lower portion of the temperature range and -the polymeriza-tion of 1,3-butadiene should take place in the upper portion of the tempera-ture range. Preferably such block polymers are obtained by first poly~
merizing isoprene or a monomer mixture containing isoprene up to a conversion of 50 to 90% of the isoprene and then continuing polymerization while adding 1,3~butadiene or a monomer mixture
- 4 1~2~3~
containing 1,3-butadiene. Thus block polymers consis-ting of th:ree blocks can be obtained.
The vulcanizable compounds according to the invention are novel since the polyisoprenes and isoprene/styrene copolymers contained therein (the rubbers according to the application) are novel.
Polyisoprenes and isoprene/styrene copolymers prepared by polymerization of monomers in amounts speciEied above are known, (German published Patent Applications 17 70 928, 24 59 357 and 28 43 794), but production is described therein as being by (almost) isothermal polymerization of isoprene or of monomer mix-tures containing isoprene. (In the examples in German Application 23 43 794, the temperature range used in producing butadiene/
styrene copolymers is between 50 and 60C.) The macromolecules thus obtained have (almost) uniform distribution of structural units obtained by 1,2 and 3,4-polymerization of isoprene. This results from the temperature-dependency o~ 1,2- and 3,4-polymeriza-tion, relative to the 1,4-polymerization of 1,3-dienes, which has been thoroughly investigated in the 1,3-butadiene example (German Patent 21 58 575)~
Because of the temperatures used in the polymerization of the polyisoprene or isoprene/styrene copolymer in accordance with the invention, more particularly the preferred range of temper-ature difference of 70 to 120C, the macromolecules obtained possess non-uniform distribution of the structural units obtained by 1,2- and 3,4-polymerization of isoprene and possibly also piperylene and 1,3-butadiene.
This means that the frequency of these s-tructural units
containing 1,3-butadiene. Thus block polymers consis-ting of th:ree blocks can be obtained.
The vulcanizable compounds according to the invention are novel since the polyisoprenes and isoprene/styrene copolymers contained therein (the rubbers according to the application) are novel.
Polyisoprenes and isoprene/styrene copolymers prepared by polymerization of monomers in amounts speciEied above are known, (German published Patent Applications 17 70 928, 24 59 357 and 28 43 794), but production is described therein as being by (almost) isothermal polymerization of isoprene or of monomer mix-tures containing isoprene. (In the examples in German Application 23 43 794, the temperature range used in producing butadiene/
styrene copolymers is between 50 and 60C.) The macromolecules thus obtained have (almost) uniform distribution of structural units obtained by 1,2 and 3,4-polymerization of isoprene. This results from the temperature-dependency o~ 1,2- and 3,4-polymeriza-tion, relative to the 1,4-polymerization of 1,3-dienes, which has been thoroughly investigated in the 1,3-butadiene example (German Patent 21 58 575)~
Because of the temperatures used in the polymerization of the polyisoprene or isoprene/styrene copolymer in accordance with the invention, more particularly the preferred range of temper-ature difference of 70 to 120C, the macromolecules obtained possess non-uniform distribution of the structural units obtained by 1,2- and 3,4-polymerization of isoprene and possibly also piperylene and 1,3-butadiene.
This means that the frequency of these s-tructural units
5 -~22~5 (and of the vinyl, isopropenyl and propenyl side groups corres-ponding to them) decreases noticeably from one end to the other along the main chain and, in the case of long-chain branches, also along the side chains of the macromolecule (cf. German Patent 21 53 575).
Thus the rubbers according to the application, especial-ly those polymerized with a difference of temperature in the pre-ferred range of temperature difference differ structurally from comparable rubbers known in the art.
In addition, they differ from comparable rubbers known in the art in their technical properties. Vulcanized products made from them have the advantage, over a wider range of tempera-tures, of resisting swelling in non-polar organic media, of damp-ing vibra-tions, and of impermeability to gases, and they also behave better in the cold. This applies, in particular, to vulcan-ized products made out of the vulcanizable compounds containing rubbers polymerized with a difference of temperature in the pre-ferred range of temperature difference and those which are having block structures and which are obtained by polymerization of the isoprene in the lower portion, and of the 1,3-butadiene in the upper portion, of the total range be-tween the starting and finishing temperatures.
The compounds according to the invention have the additional advantage that the vulcanized products made from them display a distinctly better vibra-tion-damping effect than all-purpose rubbers. They are therefore suitable for the production of structural elements used for damping vibration, especially in applications where resistance to swelling in non-polar organic J~ 6 -~;.2~Z3~
media is also required, for example mountings for buildings, machines and bridges, fenders, bumpers, buffer elements and structural elements for acoustic absorption.
Another advantage of the compounds according to the invention is that vulcanized products made from them build up rela-tively little heat under dynamic loading. They are therefore suit-able for the production of vulcanizable strip for the treads of passenger-car tires, the treads being highly non-skid and providing a high degree of comfort during travel and surprisingly low rolling resistance.
The compounds according to the invention are also suit-able for the production of materials and structural elements used to provide sealing agains-t gases, for example the inner liners of tubeless tires, also diaphragms and hoses.
In selecting the production parame-ters it should be noted that the effects of different structural units in the macro-molecules (proportion in percentage by weight) result in gradual differences in the macroscopic properties of the rubbers according to the application, i.e. (increase in Tg), the vulcanizable com-pounds and the vulcanized products made from them (improvementsin gastightness and, above all, in resistance to swelling in non-polar organic media).
The effect of the structural units corresponds to their proportion in themacromoleculesand to their specific effec-t which corresponds to the following sequence: structural units obtained by statistical copolymerization of styrene, ~ structural units obtained by 1,2- and 3,4-polymerization of isoprene or piperylene, > structural units obtained by 1,2-polymerization of 1,3-butadiene, ~2%2~
> structural units obtained by 1,4-polymerization of isoprene or piperylene, ~ s-tructural units obtained by 1,4-polymerization oE
1,3-butadiene.
The rubbers according to the application may be obtained quite simply in analogy with the corresponding produc-tion methods known in the art, including the known method of 1,2-polymerization of 1,3-butadiene (German Patent 21 58 575).
The inert organic solvent is preferably a hydrocarbon solvent.
The hydrocarbon solvent, the organolithiumcatalyst, and the cocatalyst may be those mentioned in German Patent 21 58 575.
Preferred cocatalysts are bifunctional Lewis bases.
The amounts of catalyst and cocatalyst are preferably 0.01 to 0.08 and 0.3 to 2% by weight, in relation to the monomer, the cocatalyst:catalyst weight ratio being between 5:1 and 200:1.
In order to reduce cold-flow in the rubbers according to -the application, the rubbers may be produced in the presence of divinyl-benzene as the branching agent, using preferably from 0.02 to 0.08% by weight, of divinyl-benzene in relation to the monomer.
The rubbers according to the application may be obtained by batch or continuous polymerization.
The rubbers according to the application may be used in the vulcanizable compounds alone or blended with other rubbers, especially known all-purpose rubbers, but also with special rubbers such as NBR, or with weakly unsaturated rubbers, for example EPDM
or IIR. The amount of the rubbers according to the invention used in the blend is preferably greater than 50% by weight and is govern-23~
ed by the combination of properties required for the particular application. The effect of the rubbers according to the invention in the vulcanizable compoundsl and in the vulcanized products ob-tained therefrom, corresponds to the proportion of the said rubbers contained in the blend.
The term vulcanizing agents is intended to mean known vulcanizing systems. A preferred vulcanizing system contains sulphur combined with the usual accelerators.
The amount oE vulcanizing agent to be used depends upon the other components of the mixture and may easily be determined by investigative tests.
The additives used may be Eillers conventional in rubber technology, for example carbon blacks of diEEerent activity, finely divided mineral fillers such as silicic acids, chalks, silicates and the like. The amounts used may vary very widely, depending upon the particular application.
Process oils usual in rubber technology may be used as additives, preference being given to aromatic, aliphatic and naphthenic hydrocarbons and the amounts used being governed by the particular application.
Other auxiliary agents, for example anti-agers and anti-ozone waxes, may be used in effective amounts as additives.
For the purpose of producing the compounds according to the invention from the mixture-components, and for processing them into vulcanized products, the usual apparatus of the rubber-industry for mixing, shaping and vulcanizing may be used, for example closed mixers, rolling mills, extrudersl calenders, injec--tion-moulding units, vulcanizing presses, and continuously operat-g _ ~Z~23~5i ing cross-lin]cing units.
The invention is illustrated by the following examples wherein parts are by weight and percent (%) signiEies % by weight (except in Table 3).
Production of the rubbers according to the applicatin.
400 parts of hexane, 100 parts of monomer, 0.03 parts of divinyl-benzene and ethylene-glycol dimethyl-ether, in the amounts indicated in Table 1, were placed in a stirred autoclave, any air and moisture being carefully excluded. Polymerization was initiated at 40C by the addition of n-butyl-lithium. Upon completion of the polymerization process, 0.5 parts of 2,2-methylene-bis-(4-methyl-6-tertiary butyl-phenol) was added. The solvent was separated with steam and the polymer was dried.
Table 1 Production of rubbers 1 and 2 according to the invention.
Example 1 2 Monomer Isoprene Isoprene/Styrene (80 parts/
20 parts) Ethyleneglycol-dimethylether0.5 parts 0.6 parts n-Butyllithium *)0.01 parts 0.05 parts Final Temperature 100C 90C
Polymerization Time 24 min 16 min *~ Effective amount of catalyst for polymerization.
~2~2~3~
Table 2 Characterization of rubbers 1 and 2 according to the invention.
Example 1 2 Gel Content *) 2.6~ 2.3%
1,2-Content of Dienes **) 6 % 5 %
3,4-Content of Iosprene **) 71 % 57 %
MLl+4 (100C, DIN 53 523) 100 90 Defo Elasticity (80C, DIN 53 514) 25 28 Tg (Torsional Vibration, Damping Maximum, DIN 53 520) -12C -3C
*) Determined by the method described in German Pa-tent 21 58 575.
**) Determined by IR-Analysis.
Production of the vulcanizable compounds.
The vulcanizable compounds were produced in accordance with the following formulation. A base-mixture of the following was first produced in a laboratory kneader (type GK 2):
Rubber 100 parts Carbon black N 330 50 parts Aromatic oil 5 parts VULKANOX* 4010 NA (N-phenyl-N'- 1 part isopropyl-p-phenylene-diamine) Zinc oxide 5 parts Stearic acid 2 parts After a storage period of 6 h, the vulcanizing system was incorporated, the said system consisting of Sulphur 2 parts VULKACIT* CZ 0.75 parts (N-cyclohexyl-mercaptobenzthiazole).
*Trade Mark l~ - 11 -~2~:3~L5 The rubbers used were rubbers 1 and 2 above and, for purposes of comparison, the following state-of-the-art rubbers SBR 1 500 (IISRP) (A), a eommereially available ehlorobutyl rubber (B), and a eommercially available NBR (acrylonitrile/1,3-butadiene mass ratio: 28/72) (C).
From -the eompounds 1, 2, A, B and C there were obtained, under eross-linking conditions of 40 min/150C, vulcanized test pieees 1, 2, A, B and C. They were eharacterized as follows:
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~o~
Vulcanized tes-t-pieces 1 and 2, obtained from the com-pounds according to the application, exhibit an advantageous combin-ation of properties.
They are superior to test-pieces A (based on SBR, i.e.
an all-purpose rubber) as regards resistance to swelling and gast.ightness, which properties correspond to volume-swelling and gas-permeability in Table 3. They equal tes-t-piece A in the matter of layer welding, with one layer made of compound A (based upon SBR), i.e. they exhibit similarly satisfactory covulcanization behaviour during the production of multi-layer laminated materials.
They are superior to test-pieces B (based upon a chloro-butyl rubber known -to produce vulcanized products highly imperme-able to gases) in the matter of resistance to swelling and especial-ly in the matter of layer welding. The values for gas permeability are almost as low as the corresponding values for test-piece B.
They are superior to test-pieces C (based upon an NBR, known to produce vulcanized products highly resistant to swelling in non-polar organic media) in the matter of gastightness, which is characterized by gas-permeability. The values for volume swelling do not reach the low level of the corresponding values for test-piece C, but they come comparably close.
Thus the rubbers according to the application, especial-ly those polymerized with a difference of temperature in the pre-ferred range of temperature difference differ structurally from comparable rubbers known in the art.
In addition, they differ from comparable rubbers known in the art in their technical properties. Vulcanized products made from them have the advantage, over a wider range of tempera-tures, of resisting swelling in non-polar organic media, of damp-ing vibra-tions, and of impermeability to gases, and they also behave better in the cold. This applies, in particular, to vulcan-ized products made out of the vulcanizable compounds containing rubbers polymerized with a difference of temperature in the pre-ferred range of temperature difference and those which are having block structures and which are obtained by polymerization of the isoprene in the lower portion, and of the 1,3-butadiene in the upper portion, of the total range be-tween the starting and finishing temperatures.
The compounds according to the invention have the additional advantage that the vulcanized products made from them display a distinctly better vibra-tion-damping effect than all-purpose rubbers. They are therefore suitable for the production of structural elements used for damping vibration, especially in applications where resistance to swelling in non-polar organic J~ 6 -~;.2~Z3~
media is also required, for example mountings for buildings, machines and bridges, fenders, bumpers, buffer elements and structural elements for acoustic absorption.
Another advantage of the compounds according to the invention is that vulcanized products made from them build up rela-tively little heat under dynamic loading. They are therefore suit-able for the production of vulcanizable strip for the treads of passenger-car tires, the treads being highly non-skid and providing a high degree of comfort during travel and surprisingly low rolling resistance.
The compounds according to the invention are also suit-able for the production of materials and structural elements used to provide sealing agains-t gases, for example the inner liners of tubeless tires, also diaphragms and hoses.
In selecting the production parame-ters it should be noted that the effects of different structural units in the macro-molecules (proportion in percentage by weight) result in gradual differences in the macroscopic properties of the rubbers according to the application, i.e. (increase in Tg), the vulcanizable com-pounds and the vulcanized products made from them (improvementsin gastightness and, above all, in resistance to swelling in non-polar organic media).
The effect of the structural units corresponds to their proportion in themacromoleculesand to their specific effec-t which corresponds to the following sequence: structural units obtained by statistical copolymerization of styrene, ~ structural units obtained by 1,2- and 3,4-polymerization of isoprene or piperylene, > structural units obtained by 1,2-polymerization of 1,3-butadiene, ~2%2~
> structural units obtained by 1,4-polymerization of isoprene or piperylene, ~ s-tructural units obtained by 1,4-polymerization oE
1,3-butadiene.
The rubbers according to the application may be obtained quite simply in analogy with the corresponding produc-tion methods known in the art, including the known method of 1,2-polymerization of 1,3-butadiene (German Patent 21 58 575).
The inert organic solvent is preferably a hydrocarbon solvent.
The hydrocarbon solvent, the organolithiumcatalyst, and the cocatalyst may be those mentioned in German Patent 21 58 575.
Preferred cocatalysts are bifunctional Lewis bases.
The amounts of catalyst and cocatalyst are preferably 0.01 to 0.08 and 0.3 to 2% by weight, in relation to the monomer, the cocatalyst:catalyst weight ratio being between 5:1 and 200:1.
In order to reduce cold-flow in the rubbers according to -the application, the rubbers may be produced in the presence of divinyl-benzene as the branching agent, using preferably from 0.02 to 0.08% by weight, of divinyl-benzene in relation to the monomer.
The rubbers according to the application may be obtained by batch or continuous polymerization.
The rubbers according to the application may be used in the vulcanizable compounds alone or blended with other rubbers, especially known all-purpose rubbers, but also with special rubbers such as NBR, or with weakly unsaturated rubbers, for example EPDM
or IIR. The amount of the rubbers according to the invention used in the blend is preferably greater than 50% by weight and is govern-23~
ed by the combination of properties required for the particular application. The effect of the rubbers according to the invention in the vulcanizable compoundsl and in the vulcanized products ob-tained therefrom, corresponds to the proportion of the said rubbers contained in the blend.
The term vulcanizing agents is intended to mean known vulcanizing systems. A preferred vulcanizing system contains sulphur combined with the usual accelerators.
The amount oE vulcanizing agent to be used depends upon the other components of the mixture and may easily be determined by investigative tests.
The additives used may be Eillers conventional in rubber technology, for example carbon blacks of diEEerent activity, finely divided mineral fillers such as silicic acids, chalks, silicates and the like. The amounts used may vary very widely, depending upon the particular application.
Process oils usual in rubber technology may be used as additives, preference being given to aromatic, aliphatic and naphthenic hydrocarbons and the amounts used being governed by the particular application.
Other auxiliary agents, for example anti-agers and anti-ozone waxes, may be used in effective amounts as additives.
For the purpose of producing the compounds according to the invention from the mixture-components, and for processing them into vulcanized products, the usual apparatus of the rubber-industry for mixing, shaping and vulcanizing may be used, for example closed mixers, rolling mills, extrudersl calenders, injec--tion-moulding units, vulcanizing presses, and continuously operat-g _ ~Z~23~5i ing cross-lin]cing units.
The invention is illustrated by the following examples wherein parts are by weight and percent (%) signiEies % by weight (except in Table 3).
Production of the rubbers according to the applicatin.
400 parts of hexane, 100 parts of monomer, 0.03 parts of divinyl-benzene and ethylene-glycol dimethyl-ether, in the amounts indicated in Table 1, were placed in a stirred autoclave, any air and moisture being carefully excluded. Polymerization was initiated at 40C by the addition of n-butyl-lithium. Upon completion of the polymerization process, 0.5 parts of 2,2-methylene-bis-(4-methyl-6-tertiary butyl-phenol) was added. The solvent was separated with steam and the polymer was dried.
Table 1 Production of rubbers 1 and 2 according to the invention.
Example 1 2 Monomer Isoprene Isoprene/Styrene (80 parts/
20 parts) Ethyleneglycol-dimethylether0.5 parts 0.6 parts n-Butyllithium *)0.01 parts 0.05 parts Final Temperature 100C 90C
Polymerization Time 24 min 16 min *~ Effective amount of catalyst for polymerization.
~2~2~3~
Table 2 Characterization of rubbers 1 and 2 according to the invention.
Example 1 2 Gel Content *) 2.6~ 2.3%
1,2-Content of Dienes **) 6 % 5 %
3,4-Content of Iosprene **) 71 % 57 %
MLl+4 (100C, DIN 53 523) 100 90 Defo Elasticity (80C, DIN 53 514) 25 28 Tg (Torsional Vibration, Damping Maximum, DIN 53 520) -12C -3C
*) Determined by the method described in German Pa-tent 21 58 575.
**) Determined by IR-Analysis.
Production of the vulcanizable compounds.
The vulcanizable compounds were produced in accordance with the following formulation. A base-mixture of the following was first produced in a laboratory kneader (type GK 2):
Rubber 100 parts Carbon black N 330 50 parts Aromatic oil 5 parts VULKANOX* 4010 NA (N-phenyl-N'- 1 part isopropyl-p-phenylene-diamine) Zinc oxide 5 parts Stearic acid 2 parts After a storage period of 6 h, the vulcanizing system was incorporated, the said system consisting of Sulphur 2 parts VULKACIT* CZ 0.75 parts (N-cyclohexyl-mercaptobenzthiazole).
*Trade Mark l~ - 11 -~2~:3~L5 The rubbers used were rubbers 1 and 2 above and, for purposes of comparison, the following state-of-the-art rubbers SBR 1 500 (IISRP) (A), a eommereially available ehlorobutyl rubber (B), and a eommercially available NBR (acrylonitrile/1,3-butadiene mass ratio: 28/72) (C).
From -the eompounds 1, 2, A, B and C there were obtained, under eross-linking conditions of 40 min/150C, vulcanized test pieees 1, 2, A, B and C. They were eharacterized as follows:
2~23~S
o~ ~ o oo In ~ co C) ~ O O Ln r~ O ~ ~ ~ O r~
r~r~ r~
~ ,~
~ r~ r~
a:
~ c~ n o,~ O
r-l N 1~ I ~ r ~ ,~
u~ ~ o ,~
_~
CO ~0~ r~ OO ~DIn O ~ o r~ n r-l ~ r~
In r~ r~
[~
c~ oo oo m ~ ,; 1-~ o r~
~r O
~ r- ~ co o u~
,~ ~ r~ ~ O~ O ~ ~ r~
r~ D r~
O
U~
Q o .~ 03 ~ ^ ~ o ~ o .o d~ ~ ~ 3 ~ o Q~ ~
C~ ~ -,~ ,~ ~ I
~ ~ o ~ o ~ ~
u~ ~ o 0\o ~ ~ ~ r~
r~ ~ rc; r~
a) ~ ~ ~ Z Y ~ u~
N ~ O o\ ^ a)1-- H ~ ~ r~ ~1 \
,~ _ u~ a ,~ rl IJ~ O Z
1~ 0 ^ U ~ ~ r-l r~
(~ ~(~ ~ ~ ,~1o\O ~ H I I O a) ~-1 ~ ^ U ~ U ~ o Ir) Z ~ 1 0 0 0 U~
H ~~ O E~ ~ r~ O ~ O
(~ .a ~ f~ a) o ~ ~I) O ~I U t) U
n-- o ~ In ~1----3 a o ~ o\o o~O ,~
Z O O Z -- ~ ~ O O ~ (`i O
U~ H ~ -r1 r~ r~ O
(I) 1~ ~Ln O ~~ r-l O ~ 1~ ) ~ O ~ LO
~) Q~ ZU~ 1) r-l h O
~1 .C ~ H t~r~l ~ ) U
~1) ~ o ~ LOr~ ~ ~) O 1$~
~ ~ o ~ o O ~~) o ~ Z ~1 r~ r-l n ~ U~ a) ~j i O,) rd ~rl O O H r-l ~1 ~J ~ ~ ~ U
~ ~ ~ o ~ a ~ r~ 2 - r~
O ~ i~ ~1 ~ (~ O ~ ~ ` ra O
-I UU~ O ~ ` ~ r~ -I 3 u ~a) ~ o u~ U ~ ~n o (~ ) 3 r~ Q~ ~~ (J) r~ r-l a) o a) U ~
,~ o o ra cn ~ ~ ~ r~ ~ O O ~ Q. æ
U U~ ~ O O ~ Ei ~ ~1 U ~ U~ H
Oa) r-l O ~ 0 ~ u~ O ~ ~ ~ O O ~1 ~
E~ E~ ~ ~) ~ F~ ~ ~) ~ O ~ h U ~ *
~o~
Vulcanized tes-t-pieces 1 and 2, obtained from the com-pounds according to the application, exhibit an advantageous combin-ation of properties.
They are superior to test-pieces A (based on SBR, i.e.
an all-purpose rubber) as regards resistance to swelling and gast.ightness, which properties correspond to volume-swelling and gas-permeability in Table 3. They equal tes-t-piece A in the matter of layer welding, with one layer made of compound A (based upon SBR), i.e. they exhibit similarly satisfactory covulcanization behaviour during the production of multi-layer laminated materials.
They are superior to test-pieces B (based upon a chloro-butyl rubber known -to produce vulcanized products highly imperme-able to gases) in the matter of resistance to swelling and especial-ly in the matter of layer welding. The values for gas permeability are almost as low as the corresponding values for test-piece B.
They are superior to test-pieces C (based upon an NBR, known to produce vulcanized products highly resistant to swelling in non-polar organic media) in the matter of gastightness, which is characterized by gas-permeability. The values for volume swelling do not reach the low level of the corresponding values for test-piece C, but they come comparably close.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A vulcanizable compound comprising: more than 30 to 100 parts by weight of rubber selected from the group of polyisoprenes, amorphous isoprene/styrene copolymers and mixtures thereof having a Mooney viscosity (ML1+4, 100°C DIN 53 523) of 30 to 120, a Defo elasticity (30°C, DIN 53 514) of 12 to 45, a non-homogeneity of 0.8 to 5.5, and a glass transition temperature (Tg, torsional vibration, damping maximum, DIN 53 520) between -35 and 0°C; 0 to less than 70 parts by weight of another rubber or a mix-ture of other rubbers per 100 parts by weight of rubber, an effec-tive amount of a vulcanizing agent, wherein the polyisoprenes is ob-tained by homopolymerization of isoprene or by polymerization of a monomer mixture of 55 to less than 100% by weight of isoprene 0 to 20% by weight of piperylene, 0 to 45% by weight of 1,3-butadiene, and 0 to less than 1% by weight of styrene in relation to the mono-mer mixture, the said polyisoprene containing an average of between 60 and 85% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes; or the isoprene/styrene copolymer is obtained by polymerization of a monomer mixture of 35 to 99% by weight of isoprene, 1 to 30% by weight of styrene, 0 to 25% by weight of piperylene, and 0 to less than 50% by weight of 1,3-buta-diene in relation to the monomer mixture, and having an average con-tent of 55 to 90% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes and statistical copolymerization of styrene, the polymerization of the said polyisoprene or isoprene/
styrene copolymer being characterized by the following conditions:
polymerization in an inert organic solvent in the presence of a catalyst system consisting of an amount effective for polymerization of 0.008 to 0.1% by weight of an organolithium catalyst and 0.1 to 10% by weight of a cocatalyst selected from the group of ethers, tertiary amines and mixtures thereof, the weight ratio of cocatalyst : catalyst being between 2 : 1 and 1 000 : 1, and in the presence of 0 to 0.1% by weight of divinyl-benzene, related respectively to the monomer, and the polymerization of the polyisoprene or the isoprene/styrene copolymer is carried out at an increasing temperature, starting at between 15 and 50°C and finishing at 70 to 145°C, and the difference between the finishing and starting temperatures being between 40 and 125°C.
styrene copolymer being characterized by the following conditions:
polymerization in an inert organic solvent in the presence of a catalyst system consisting of an amount effective for polymerization of 0.008 to 0.1% by weight of an organolithium catalyst and 0.1 to 10% by weight of a cocatalyst selected from the group of ethers, tertiary amines and mixtures thereof, the weight ratio of cocatalyst : catalyst being between 2 : 1 and 1 000 : 1, and in the presence of 0 to 0.1% by weight of divinyl-benzene, related respectively to the monomer, and the polymerization of the polyisoprene or the isoprene/styrene copolymer is carried out at an increasing temperature, starting at between 15 and 50°C and finishing at 70 to 145°C, and the difference between the finishing and starting temperatures being between 40 and 125°C.
2. A vulcanizable compound according to claim 1, wherein the polyisoprene or isoprene/styrene copolymer possesses a Mooney visco-sity of 40 to 100, a Defo elasticity of 20 to 40, a non-homogeneity of 1 to 4, and a glass transition temperature between -30 and -5°C.
3. A vulcanizable compound according to claim 1, wherein the polyisoprene is obtained by polymerization of a monomer mixture con-sisting of 65 to 90% by weight of isoprene, 0 to 10% by weight of piperylene, 0 to 35% by weight of 1,3-butadiene, and 0 to less than 1% by weight of styrene, in relation to the monomer mixture, and has an average content of 65 to 80% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes, or the isoprene/styrene copolymer is obtained by polymerization of a monomer mixture consisting of 40 to 90% by weight of isoprene, 10 to 25% by weight of styrene, 0 to 15% by weight of piperylene, and 0 to 40% by weight of 1,3-buta-diene, in relation to the monomer mixture, with an average content of 60 to 85%
by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes and by statistical copolymerization of styrene.
by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes and by statistical copolymerization of styrene.
4. A vulcanizable compound according to claim 2, wherein the polyisoprene is obtained by polymerization of a monomer mixture consisting of 65 to 90% by weight of isoprene, 0 to 10% by weight of piperylene, 0 to 35% by weight of 1,3-butadiene, and 0 to less than 1% by weight of styrene, in relation to the monomer mixture, and has an average content of 65 to 80% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes, or the isoprene/styrene copolymer is obtained by polymerization of a monomer mixture consisting of 40 to 90% by weight of isoprene, 10 to 25% by weight of styrene, 0 to 15% by weight of piperylene, and 0 to 40% by weight of 1,3-butadiene, in relation to the monomer mix-ture, with an average content of 60 to 85% by weight of structural units obtained by 1,2- and 3,4-polymerization of the dienes and by statistical copolymerization of styrene.
5. A vulcanizable compound according to claim 3 or 4, where-in the polyisoprene or isoprene/styrene copolymer exhibits a statis-tical distribution of the structural units corresponding to the different monomers, the difference between the finishing and start-ing temperatures during the polymerization amounting to between 70 and 120°C and the said polymerization terminating at between 85 and 145°C.
6. A vulcanizable compound according to claim 3 or 4 where-in the polyisoprene or isoprene/styrene copolymer exhibits block-structures, provided that the isoprene/styrene copolymer does not contain homopolymerized blocks of styrene.
7. A vulcanizable compound according to claim 3 or 4 where-in the polyisoprene or isoprene/styrene copolymer exhibits block-structures, provided that the isoprene/styrene copolymer does not contain homopolymerized blocks of styrene, the polyisoprene or isoprene/styrene copolymer with block-structure being obtained by polymerization of the isoprene in the lower portion, and of the 1,3-butadiene in the upper portion, of the total range between the starting and finishing temperatures.
8. A vulcanizable compound according to claim 3 or 4 where-in the polyisoprene or isoprene/styrene copolymer exhibits block-structures, provided that the isoprene/styrene copolymer does not contain homopolymerized blocks of styrene, the polyisoprene or isoprene/styrene copolymer with block-structure being obtained by polymerization of the isoprene in the lower portion, and of the 1,3-butadiene in the upper portion, of the total range between the starting and finishing temperatures, and wherein 1,3-butadiene, or a monomer mixture containing 1,3-butadiene, is added to the iso-prene or to a monomer mixture containing isoprene, the addition being initiated after 50 to 90% isoprene conversion.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3220151.6 | 1982-05-28 | ||
| DE3220151 | 1982-05-28 | ||
| DE19833310118 DE3310118A1 (en) | 1982-05-28 | 1983-03-21 | VULCANIZABLE MEASURES |
| DEP3310118.3 | 1983-03-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1222345A true CA1222345A (en) | 1987-05-26 |
Family
ID=25802083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428996A Expired CA1222345A (en) | 1982-05-28 | 1983-05-26 | Vulcanizable compounds |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0095629B1 (en) |
| CA (1) | CA1222345A (en) |
| DE (2) | DE3310118A1 (en) |
| ES (1) | ES522755A0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2346887A (en) * | 1999-02-12 | 2000-08-23 | Goodyear Tire & Rubber | Liquid isoprene-butadiene rubber |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3424732C1 (en) * | 1984-07-05 | 1985-11-21 | Hüls AG, 4370 Marl | Heat-vulcanizable treads for the production of treads for automotive pneumatic tires |
| DE3707434A1 (en) * | 1986-05-31 | 1987-12-03 | Huels Chemische Werke Ag | POLYISOPRENE WITH A HIGH QUANTITY OF 1,2- AND 3,4-STRUCTURAL UNITS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3705761A1 (en) * | 1987-02-24 | 1988-09-01 | Uniroyal Englebert Gmbh | TUBELESS AIR TIRE |
| US5191021A (en) * | 1988-06-29 | 1993-03-02 | The Goodyear Tire & Rubber Company | Tire with tread containing styrene, isoprene, butadiene terpolymer rubber |
| US5047483A (en) * | 1988-06-29 | 1991-09-10 | The Goodyear Tire & Rubber Company | Pneumatic tire with tread of styrene, isoprene, butadiene rubber |
| US5254653A (en) * | 1989-12-28 | 1993-10-19 | The Goodyear Tire & Rubber Company | Terpolymer rubber of styrene, isoprene and butadiene |
| US5159020A (en) * | 1989-12-28 | 1992-10-27 | The Goodyear Tire & Rubber Company | Tire with tread comprising styrene, isoprene, butadiene terpolymer rubber |
| US5231153A (en) * | 1992-04-06 | 1993-07-27 | The Goodyear Tire & Rubber Company | Anionic polymerization of conjugated dienes modified with alkyltetrahydrofurfuryl ethers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1958650A1 (en) * | 1969-11-22 | 1971-05-27 | Huels Chemische Werke Ag | Process for polymerizing butadiene (1,3) with organolithium compounds and polybutadienes obtained thereafter |
| DE2158575C3 (en) * | 1971-11-26 | 1981-03-12 | Chemische Werke Hüls AG, 4370 Marl | Process for the production of block homopolymers of butadiene (1.3) |
| FR2255313B1 (en) * | 1973-12-20 | 1976-10-08 | Gole Jean | |
| GB1604395A (en) * | 1977-10-08 | 1981-12-09 | Dunlop Ltd | Elastomer compositions and tyre treads comprising them |
-
1983
- 1983-03-21 DE DE19833310118 patent/DE3310118A1/en active Granted
- 1983-05-13 DE DE8383104740T patent/DE3371350D1/en not_active Expired
- 1983-05-13 EP EP83104740A patent/EP0095629B1/en not_active Expired
- 1983-05-26 CA CA000428996A patent/CA1222345A/en not_active Expired
- 1983-05-27 ES ES522755A patent/ES522755A0/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2346887A (en) * | 1999-02-12 | 2000-08-23 | Goodyear Tire & Rubber | Liquid isoprene-butadiene rubber |
| GB2346887B (en) * | 1999-02-12 | 2003-01-15 | Goodyear Tire & Rubber | Liquid isoprene-butadiene rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0095629B1 (en) | 1987-05-06 |
| DE3310118A1 (en) | 1983-12-01 |
| EP0095629A3 (en) | 1984-03-28 |
| DE3371350D1 (en) | 1987-06-11 |
| EP0095629A2 (en) | 1983-12-07 |
| ES8500629A1 (en) | 1984-03-16 |
| DE3310118C2 (en) | 1990-08-02 |
| ES522755A0 (en) | 1984-03-16 |
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