CA2236010A1 - New terpolymers of isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds - Google Patents
New terpolymers of isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds Download PDFInfo
- Publication number
- CA2236010A1 CA2236010A1 CA002236010A CA2236010A CA2236010A1 CA 2236010 A1 CA2236010 A1 CA 2236010A1 CA 002236010 A CA002236010 A CA 002236010A CA 2236010 A CA2236010 A CA 2236010A CA 2236010 A1 CA2236010 A1 CA 2236010A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- unsaturated organic
- butene
- terpolymer
- isoolefin
- 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.)
- Abandoned
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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—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
- C08F236/04—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides new rubber-like terpolymers comprising isoolefins, conjugated diolefins and other singly or multiply unsaturated organic compounds and a process for producing the new terpolymers. The new terpolymers are used to produce rubber vulcanizates, particularly tyres.
Description
New terpol~mers of isoolefins~ coniu~ated (liol~fin~ and sin~lv or multiplv unsaturated or~anic compounds The present invention provides new rubber-like terpolymers comprising isoolefins, conjugated diolefins and other singly or multiply unsaturated organic compounds and a process for producing the new terpolymers.
Block copolymers of (A) isobutene, C3-CI2 olefins and conjugated dienes and (B) cationically or anionically polymerizable monomers, such as styrene or acrylates, are known (JP-05 295 054). Because of their block structure these copolymers exhibit poor co-vulcanization performance and are not therefore suitable for use in the tyre field.
Copolymers comprising at least one C2-C7-a olefin, such as isobutene, ethene or propene, and at least one C4-CI4 diolefin, such as butadiene, isoprene or cyclopentadiene are also lS known (DE-A-01 595 573). These copolymers are characterized by a very low molecular weight (M, = 3000 to I 5,000 g/mol) and are not therefore suitable for use in the tyre field.
Furthermore, copolymers of isobutene, a diolefin such as butadiene or isoprene, and a cationically polymerizable aromatic monomer, such as styrene, a-methylstyrene ordivinylbenzene are known (DE 883 354, Canadian patent 464 086, US 2 539 523). For the polymers the examples described in these patent publications predorninantly show molecular weights in the range from 5000 to 60000 and they are therefore only suitable for applications as adhesive and sealing compounds, but not for use in the tyre field.
The present invention provides new rubber-like terpolymers comprising isoolefins with 4 to 16 carbon atoms, conjugated diolefins with 4 to 6 carbon atoms and other singly or multiply unsaturated organic compounds with 2 to 20 carbon atoms with a molecular weightM w of 50,000 to 2,000,000 g/mol, preferably 100,000 to 1,000,000 g/mol, wherein the molar ratio adding up to 100 between isoolefins and diolefins and unsaturated organic compounds is 50-99:0.546.5:0.5-49.5, preferably 60-98: 1.5-20:0.5-20.
Those isoolefins with 4-16 carbon atoms, such as isobutene, 2-methyl-1-butene, 2,3-dimetllyl-l-butene, 2-methyl-1-pentene and b-pinene, are preferably considered, particu-larly isobutene and 2-methyl- 1 -butene.
5 (~onju~ate(l diolel;lls whicll mcly pr~lèl-al~ly be melllioned arc isoprelle, bulLIdiellc, 2,3-dimetllyl butadiene, cyclopentadiene, methylcyclopentadiene, l,3-cyclohexadielle, particu-larly isoprene.
Olefins which cannot be cationically polymerized, or can only be cationically polymerized 10 with great difficulty, are considered as singly or multiply unsaturated organic compounds, prelèrably l-olefins witll 2 to 20 carbon atoms, such as ethene, propene, I-butelle, 1-pentene, I-hexene, I-heptene, I-octene, I-nonene, I-decene, 5-vinyl-2-nolbornene, par-ticularly ethene and propene.
I S The terpolymers according to the invention have a Mooney viscosity of 30-100, preferably 45-80, a gel content of 0% to 50%, preferably 0.5-5%, and an intrinsic viscosity of 0.5-2, preferably 1-1.5.
The present invention further provides a process for producing the terpolymers described 20 above, which is characterized in that isoolefins with 4 to 16 carbon atoms are polymerized with conjugated diolefins with 4 to 6 carbon atoms and singly or multiply unsaturated organic compounds with 2 to 20 carbon atoms in the presence of an initiatol system based on vanadium tetrachloridelhydrocarbon solutions at temperatures of -100~C to + 100~C, preferably -70~C to 0~C and pressures of 0.001 to 70 bars, preferably 0.01-10, wherein the 25 molar ratio adding up to 100 between isoolefins and diolefins and unsaturated organic compounds is 50-99:0.5-46.5:0.549.5, preferably 60-98:1.5-20:0.5-20.
The process according to the invention may be carried out botll continuously anddiscontinuously. Polymerization may take place in solution, in bulk, in suspension and in 30 the gaseous phase.
The initiator system based on v~n~ m tetrachloride/hydrocarbon solutions for producing the terpolyrners according to the invention is known and described in German patent application DE-A 19 627 529.
For the polymerization according to the invention it is very important to use definedly aged vanadium tetrachloride/hydrocarbon solutions, optionally in combination with a co-initiator, as described in the above-mentioned German patent application.
Suitable solvents for polymerization according to the invention are aliphatic and/or aromatic (optionally halogenated) hydrocarbons with no functional substituents. Solvents with a melting point below 20~C are preferanly used, solvents with a melting point below 0~C are particularly preferably used.
Examples of suitable (aliphatic) solvents are: methyl chloride, methylene chloride, chloro-form, carbon tetrachloride, pentane, hexane, 2,3-dimethylbutane, heptane, cyclohexane, methylcyclohexane, chloroethane, I,l-dichloroethane, 1,2-dichloroethane, I,l,1-trichloro-ethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,2,3-trichloropropane, 1-chlorobutane, 2-chloro-butane, 1,4-dichlorobutane, 1-chloro-2-methylpropane, 1-chloropentane, 2,4-dimethyl-pentane, 2,2,4-trimethylpentane, dodecane, 1-chlorododecane, petroleum ether, chloro-cyclohexane, cyclododecane, decalin.
Examples of aromatic solvents are: benzene, toluene, chlorobenzene, 1,2-dichloro-benzene, ethylbenzene, xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-tri-methylbenzene, diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, 1-isopropyl-4-methylbenzene, 1,3-diiso-propylbenzene, 1,4-diisopropylbenzene, 1-tert.-butyl-3,5-dimethylbenzene, 1,3,5-triiso-propylbenzene.
Block copolymers of (A) isobutene, C3-CI2 olefins and conjugated dienes and (B) cationically or anionically polymerizable monomers, such as styrene or acrylates, are known (JP-05 295 054). Because of their block structure these copolymers exhibit poor co-vulcanization performance and are not therefore suitable for use in the tyre field.
Copolymers comprising at least one C2-C7-a olefin, such as isobutene, ethene or propene, and at least one C4-CI4 diolefin, such as butadiene, isoprene or cyclopentadiene are also lS known (DE-A-01 595 573). These copolymers are characterized by a very low molecular weight (M, = 3000 to I 5,000 g/mol) and are not therefore suitable for use in the tyre field.
Furthermore, copolymers of isobutene, a diolefin such as butadiene or isoprene, and a cationically polymerizable aromatic monomer, such as styrene, a-methylstyrene ordivinylbenzene are known (DE 883 354, Canadian patent 464 086, US 2 539 523). For the polymers the examples described in these patent publications predorninantly show molecular weights in the range from 5000 to 60000 and they are therefore only suitable for applications as adhesive and sealing compounds, but not for use in the tyre field.
The present invention provides new rubber-like terpolymers comprising isoolefins with 4 to 16 carbon atoms, conjugated diolefins with 4 to 6 carbon atoms and other singly or multiply unsaturated organic compounds with 2 to 20 carbon atoms with a molecular weightM w of 50,000 to 2,000,000 g/mol, preferably 100,000 to 1,000,000 g/mol, wherein the molar ratio adding up to 100 between isoolefins and diolefins and unsaturated organic compounds is 50-99:0.546.5:0.5-49.5, preferably 60-98: 1.5-20:0.5-20.
Those isoolefins with 4-16 carbon atoms, such as isobutene, 2-methyl-1-butene, 2,3-dimetllyl-l-butene, 2-methyl-1-pentene and b-pinene, are preferably considered, particu-larly isobutene and 2-methyl- 1 -butene.
5 (~onju~ate(l diolel;lls whicll mcly pr~lèl-al~ly be melllioned arc isoprelle, bulLIdiellc, 2,3-dimetllyl butadiene, cyclopentadiene, methylcyclopentadiene, l,3-cyclohexadielle, particu-larly isoprene.
Olefins which cannot be cationically polymerized, or can only be cationically polymerized 10 with great difficulty, are considered as singly or multiply unsaturated organic compounds, prelèrably l-olefins witll 2 to 20 carbon atoms, such as ethene, propene, I-butelle, 1-pentene, I-hexene, I-heptene, I-octene, I-nonene, I-decene, 5-vinyl-2-nolbornene, par-ticularly ethene and propene.
I S The terpolymers according to the invention have a Mooney viscosity of 30-100, preferably 45-80, a gel content of 0% to 50%, preferably 0.5-5%, and an intrinsic viscosity of 0.5-2, preferably 1-1.5.
The present invention further provides a process for producing the terpolymers described 20 above, which is characterized in that isoolefins with 4 to 16 carbon atoms are polymerized with conjugated diolefins with 4 to 6 carbon atoms and singly or multiply unsaturated organic compounds with 2 to 20 carbon atoms in the presence of an initiatol system based on vanadium tetrachloridelhydrocarbon solutions at temperatures of -100~C to + 100~C, preferably -70~C to 0~C and pressures of 0.001 to 70 bars, preferably 0.01-10, wherein the 25 molar ratio adding up to 100 between isoolefins and diolefins and unsaturated organic compounds is 50-99:0.5-46.5:0.549.5, preferably 60-98:1.5-20:0.5-20.
The process according to the invention may be carried out botll continuously anddiscontinuously. Polymerization may take place in solution, in bulk, in suspension and in 30 the gaseous phase.
The initiator system based on v~n~ m tetrachloride/hydrocarbon solutions for producing the terpolyrners according to the invention is known and described in German patent application DE-A 19 627 529.
For the polymerization according to the invention it is very important to use definedly aged vanadium tetrachloride/hydrocarbon solutions, optionally in combination with a co-initiator, as described in the above-mentioned German patent application.
Suitable solvents for polymerization according to the invention are aliphatic and/or aromatic (optionally halogenated) hydrocarbons with no functional substituents. Solvents with a melting point below 20~C are preferanly used, solvents with a melting point below 0~C are particularly preferably used.
Examples of suitable (aliphatic) solvents are: methyl chloride, methylene chloride, chloro-form, carbon tetrachloride, pentane, hexane, 2,3-dimethylbutane, heptane, cyclohexane, methylcyclohexane, chloroethane, I,l-dichloroethane, 1,2-dichloroethane, I,l,1-trichloro-ethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,2,3-trichloropropane, 1-chlorobutane, 2-chloro-butane, 1,4-dichlorobutane, 1-chloro-2-methylpropane, 1-chloropentane, 2,4-dimethyl-pentane, 2,2,4-trimethylpentane, dodecane, 1-chlorododecane, petroleum ether, chloro-cyclohexane, cyclododecane, decalin.
Examples of aromatic solvents are: benzene, toluene, chlorobenzene, 1,2-dichloro-benzene, ethylbenzene, xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-tri-methylbenzene, diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, 1-isopropyl-4-methylbenzene, 1,3-diiso-propylbenzene, 1,4-diisopropylbenzene, 1-tert.-butyl-3,5-dimethylbenzene, 1,3,5-triiso-propylbenzene.
3 0 The aromatic compounds optionally used as co-initiators are characterized in that they are polycyclic (at least bicyclic) aromatic and/or heteroaromatic hydrocarbons which may be substituted by alkyl or alkenyl groups. Bi, tri and tetracyclic systems are preferred.
Examples of suitable compounds are: naphthalene, anthracene, indene, benzofuran, carba-zole, n-vinylcarbazole, biphenyl, p-terphenyl, acenaphthene, acenaphthylene, fiuoranthene, fluorene, phen:~nthrene, pyrene or octylated diphenylamine (Vulkanox OCD from BAYER).
5 The conditions for the ageing of the initiator depend on the solvent used. Suitable solvents for the ageing of the initiator in the me~ning of the invention are hydrocarbons, particularly aliphatic and aromatic hydrocarbons with no functional substituents with 4 to 20 carbon atoms and with a boiling point above -20~C. Solvents with a melting point below 20~C
are preferred, solvents with a melting point below 0~C are particularly preferred.
10 Examples of hydrocarbons are: pentane, hexane, 2,3-dimethylbutane, heptane, cyclo-pentane and/or methylcyclohexane; pentane and hexane are particularly preferred.
In principle the ageing of the initiator may take place in a wide temperature range and is basically only restricted by the melting point and the boiling point of the solvent used. A
temperature range of 0 to 40~C is preferred, + 10 to + 30~C is particularly preferred.
Ageing may take place in the presence of light or in the dark.
Daylight is preferred; artificial light (in the visible or ultraviolet range) (e.g. incandescent lamp or mercury discharge lamp) may also be used.
The optimum ageing time depends on the solvent used, the temperature, the amount of light and the concentration of the solvent. Ageing times of a few minutes to several weeks are possible; ageing times of a few hours to a few days are preferred, ageing times of an hour up to 24 hours are particularly preferred.
During ageing the concentration of the v~n~ m tetrachloride may vary from 0.01 mmol per litre of solvent to 10 mol per litre of solvent. The initiator may be aged in the presence or absence of the co-initiator. In a preferred embodiment, ageing takes place in the absence of the co-initiator. The aged initiator may be directly used to initiate polymeri-30 zation or be subjected to a filtration in order to separate offinsoluble constituents.
To remove impurities, particularly moisture, alkali and alkaline earth metals, their~m~lg~ms with mercury or hydrogen compounds of the metals of groups I, II III and IV
of the periodic system (Mendeleev) may optionally be added to the monomer mixture as drying agents.
The quantity of initiator which is used in the process according to the invention is 0.001 mmol to 100 mmol, preferably 0.01 mmol per mol of isoolefin. The most suitable quantity may be determined by corresponding preliminary trials in each case.
The quantity of solvent is 0.1 to 50 kg, preferably 0.1 to 10 kg per kg of monomer mixture.
In this case also, the most favourable quantity of solvent may easily be deterrnined by corresponding prelirninary trials.
In a preferred embodiment the process according to the invention is carried out discontinuously as follows for example: the solvent, co-initiator and monomers are placed into the reactor which has already been cooled to reaction temperature. The initiator is then pumped in at a rate of I ml per hour to 1000 ml per hour, until an exothermic reaction begins. All operations are carried out with protective gas or a slight vacuum.
The progress of the reaction is followed with the aid of the evolution of heat. When the exotherrnic reaction has ended, 2,6-di-tert.-butyl4-methyl-phenol dissolved in ethanol is used to stop and the corresponding terpolymer is isolated.
It is surprising that new rubber-like terpolymers comprising isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds which have a very high molecular weight and may therefore be used particularly satisfactorily for tyre m~m~f~cture for example can be produced with the process according to the invention. The physical properties of the terpolymers are comparable with known copolymers based on isoolefins and diolefins; the processing properties are also very favourable, as is shown by the corresponding Mooney viscosities.
F,Y~r P'~S
The gel contents were determined in toluene after a dissolving time of 24 hours at 30~C
with a sample concentration of 12.5 g/l. The insoluble constituents were separated offby ultracentrifuging (1 hour at 20,000 rpm and 25~C).
The solution viscosity h of the soluble constituents was determined in toluene at 30~C by Ubbelohde capillary viscosimetry.
10 The molecular weight Mv calculated from the solution viscosity was determined according to the following formula: ln (Mv) = 12.48 + 1.565 * ln h.
Measurement of the Mooney viscosities took place after 8 minutes at a temperature of 125~C.
Measurement of the UV spectra of the catalyst solutions was carried out with a Perkin-Elmer W spectrometer at room temperature with an llntlilllted catalyst solution in a cell with 0.01 mm layer thickness.
20 Unless otherwise stated, before use the solvents used were distilled over calcium hydride in an argon atmosphere to purify them.
The isobutene used in the polymerizations was passed through a column filled with sodium on aluminium oxide for drying purposes, To remove the stabilizer the isoprene used was filtered through a column with dried ~luminium oxide accompanied by argon and used in this form for the polymerization, Before use the other comonomers used were distilled over calcium hydride in an argon 3 0 atmosphere to purify them, The incorporation rate and the type of incorporation of the di~lell~ monomers was determined by IH-NMR and l3C-NMR
Example 1 s 500 ml of hexane were presented accompanied by argon. 24.1 g (0.125 mol) of V~ln~f~ m tetrachloride were added. The solution was exposed to daylight for seven days accompanied by light agitation, and a distinct deepening of the red coloration and the occurrence of small quantities of a solid were observed. The extent of this colour change 10 can be seen from the comparison of the UV spectra which are shown alongside each other in the graph below.
UV spectra as a function of ageing time UV spectra as function of ageing time 4ls~
Examples of suitable compounds are: naphthalene, anthracene, indene, benzofuran, carba-zole, n-vinylcarbazole, biphenyl, p-terphenyl, acenaphthene, acenaphthylene, fiuoranthene, fluorene, phen:~nthrene, pyrene or octylated diphenylamine (Vulkanox OCD from BAYER).
5 The conditions for the ageing of the initiator depend on the solvent used. Suitable solvents for the ageing of the initiator in the me~ning of the invention are hydrocarbons, particularly aliphatic and aromatic hydrocarbons with no functional substituents with 4 to 20 carbon atoms and with a boiling point above -20~C. Solvents with a melting point below 20~C
are preferred, solvents with a melting point below 0~C are particularly preferred.
10 Examples of hydrocarbons are: pentane, hexane, 2,3-dimethylbutane, heptane, cyclo-pentane and/or methylcyclohexane; pentane and hexane are particularly preferred.
In principle the ageing of the initiator may take place in a wide temperature range and is basically only restricted by the melting point and the boiling point of the solvent used. A
temperature range of 0 to 40~C is preferred, + 10 to + 30~C is particularly preferred.
Ageing may take place in the presence of light or in the dark.
Daylight is preferred; artificial light (in the visible or ultraviolet range) (e.g. incandescent lamp or mercury discharge lamp) may also be used.
The optimum ageing time depends on the solvent used, the temperature, the amount of light and the concentration of the solvent. Ageing times of a few minutes to several weeks are possible; ageing times of a few hours to a few days are preferred, ageing times of an hour up to 24 hours are particularly preferred.
During ageing the concentration of the v~n~ m tetrachloride may vary from 0.01 mmol per litre of solvent to 10 mol per litre of solvent. The initiator may be aged in the presence or absence of the co-initiator. In a preferred embodiment, ageing takes place in the absence of the co-initiator. The aged initiator may be directly used to initiate polymeri-30 zation or be subjected to a filtration in order to separate offinsoluble constituents.
To remove impurities, particularly moisture, alkali and alkaline earth metals, their~m~lg~ms with mercury or hydrogen compounds of the metals of groups I, II III and IV
of the periodic system (Mendeleev) may optionally be added to the monomer mixture as drying agents.
The quantity of initiator which is used in the process according to the invention is 0.001 mmol to 100 mmol, preferably 0.01 mmol per mol of isoolefin. The most suitable quantity may be determined by corresponding preliminary trials in each case.
The quantity of solvent is 0.1 to 50 kg, preferably 0.1 to 10 kg per kg of monomer mixture.
In this case also, the most favourable quantity of solvent may easily be deterrnined by corresponding prelirninary trials.
In a preferred embodiment the process according to the invention is carried out discontinuously as follows for example: the solvent, co-initiator and monomers are placed into the reactor which has already been cooled to reaction temperature. The initiator is then pumped in at a rate of I ml per hour to 1000 ml per hour, until an exothermic reaction begins. All operations are carried out with protective gas or a slight vacuum.
The progress of the reaction is followed with the aid of the evolution of heat. When the exotherrnic reaction has ended, 2,6-di-tert.-butyl4-methyl-phenol dissolved in ethanol is used to stop and the corresponding terpolymer is isolated.
It is surprising that new rubber-like terpolymers comprising isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds which have a very high molecular weight and may therefore be used particularly satisfactorily for tyre m~m~f~cture for example can be produced with the process according to the invention. The physical properties of the terpolymers are comparable with known copolymers based on isoolefins and diolefins; the processing properties are also very favourable, as is shown by the corresponding Mooney viscosities.
F,Y~r P'~S
The gel contents were determined in toluene after a dissolving time of 24 hours at 30~C
with a sample concentration of 12.5 g/l. The insoluble constituents were separated offby ultracentrifuging (1 hour at 20,000 rpm and 25~C).
The solution viscosity h of the soluble constituents was determined in toluene at 30~C by Ubbelohde capillary viscosimetry.
10 The molecular weight Mv calculated from the solution viscosity was determined according to the following formula: ln (Mv) = 12.48 + 1.565 * ln h.
Measurement of the Mooney viscosities took place after 8 minutes at a temperature of 125~C.
Measurement of the UV spectra of the catalyst solutions was carried out with a Perkin-Elmer W spectrometer at room temperature with an llntlilllted catalyst solution in a cell with 0.01 mm layer thickness.
20 Unless otherwise stated, before use the solvents used were distilled over calcium hydride in an argon atmosphere to purify them.
The isobutene used in the polymerizations was passed through a column filled with sodium on aluminium oxide for drying purposes, To remove the stabilizer the isoprene used was filtered through a column with dried ~luminium oxide accompanied by argon and used in this form for the polymerization, Before use the other comonomers used were distilled over calcium hydride in an argon 3 0 atmosphere to purify them, The incorporation rate and the type of incorporation of the di~lell~ monomers was determined by IH-NMR and l3C-NMR
Example 1 s 500 ml of hexane were presented accompanied by argon. 24.1 g (0.125 mol) of V~ln~f~ m tetrachloride were added. The solution was exposed to daylight for seven days accompanied by light agitation, and a distinct deepening of the red coloration and the occurrence of small quantities of a solid were observed. The extent of this colour change 10 can be seen from the comparison of the UV spectra which are shown alongside each other in the graph below.
UV spectra as a function of ageing time UV spectra as function of ageing time 4ls~
4 ' ~\ I catalystsolution, not aged ', \ ' ' ' catalyst solution, aged for 1 week 3 _ I \ ~~~ VOC13, unaqed 2 5 - I \
-O,5 1 ~ I I I I !
nm The solid which had settled (<' 1%) was filtered off accompanied by argon. The remaining solution was kept under argon and used in this form to initiate polymerization.
If properly kept, this solution can be used for several weeks. Any slight turbidity which may occur during storage can be removed by filtration.
Example 2 400 g (7.14 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 100 g (2.376 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Light was excluded and 6.4 ml of an initiator solution produced according to Example 1 were added dropwise within 15 minutes. After 30 minutes the 10 weakly exotherrnic reaction was stopped because of the increasing viscosity, by adding a pre-cooled solution of 1 g of 2,2'-methylene-bis(4-methyl-6-tert.-butylphenol) (Vulkanox BKF from Bayer AG, Leverkusen) in 250 ml of ethanol. After the liquid had been deç~nted off the settled polyrner was washed with 2.5 l of methanol, rolled out to a thin sheet and dried in vacuo for one day at 50~C (yield: 157 g = 30.6%).
The colourless polymer obtained in this way had a Mooney value of 52.5, a gel content of 46% and an intrinsic viscosity of 0.75 dl/g. Mv = 167,700.
The following monomer contents were determined by NMR measurements:
Isoprene 2.5 +/- 0.2 mol%
Isobutene 87.7 +/- 0.9 mol%
Propene 9.8 +/- 0.9 mol%
Ex~lmple 3 300 g (5.35 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 200 g (4.752 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Polymerization took place according to the conditions ofExample 2. Yeld: 45.5 g = 8.9%.
The colourless polymer obtained in this way had a Mooney value of 12, a gel content of 42% and an intrinsic viscosity of 0.217 dl/g. Mv = 24,100.
The following monomer contents were deterrnined by NMR measurements:
Isoprene 3.6 +/- 0.2 mol%
-O,5 1 ~ I I I I !
nm The solid which had settled (<' 1%) was filtered off accompanied by argon. The remaining solution was kept under argon and used in this form to initiate polymerization.
If properly kept, this solution can be used for several weeks. Any slight turbidity which may occur during storage can be removed by filtration.
Example 2 400 g (7.14 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 100 g (2.376 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Light was excluded and 6.4 ml of an initiator solution produced according to Example 1 were added dropwise within 15 minutes. After 30 minutes the 10 weakly exotherrnic reaction was stopped because of the increasing viscosity, by adding a pre-cooled solution of 1 g of 2,2'-methylene-bis(4-methyl-6-tert.-butylphenol) (Vulkanox BKF from Bayer AG, Leverkusen) in 250 ml of ethanol. After the liquid had been deç~nted off the settled polyrner was washed with 2.5 l of methanol, rolled out to a thin sheet and dried in vacuo for one day at 50~C (yield: 157 g = 30.6%).
The colourless polymer obtained in this way had a Mooney value of 52.5, a gel content of 46% and an intrinsic viscosity of 0.75 dl/g. Mv = 167,700.
The following monomer contents were determined by NMR measurements:
Isoprene 2.5 +/- 0.2 mol%
Isobutene 87.7 +/- 0.9 mol%
Propene 9.8 +/- 0.9 mol%
Ex~lmple 3 300 g (5.35 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 200 g (4.752 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Polymerization took place according to the conditions ofExample 2. Yeld: 45.5 g = 8.9%.
The colourless polymer obtained in this way had a Mooney value of 12, a gel content of 42% and an intrinsic viscosity of 0.217 dl/g. Mv = 24,100.
The following monomer contents were deterrnined by NMR measurements:
Isoprene 3.6 +/- 0.2 mol%
5 Isobutene 81.0 +/- 0.5 mol%
Propene 15.4 +/- 0.5 mol%
Example 4 (comparative ~Y~ p'~) 200 g (3.57 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 300 g (7.128 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Polymerization took place according to the conditions ofExample 2. ~leld: 3.4 g = 0.7%.
15 The polymer was not investigated further because of the low yield. This example clearly shows the trend, which was already identifiable in Example 3, towards a reduction of the yield and Mooney value as the propene concentration increases.
Example 5 400 g (7.14 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 100 g (0.83 mol) of 5-vinyl-2-norbornene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of 40~C in an argon atmosphere. Polym~ri7~tion took place according to the conditions of Example 2. Yield: 53.7 g= 10.5%.
The slightly brown polymer obtained in this way had a gel content of 0.5% and an intrinsic viscosity of 0.391 dVg. Mv = 60,500.
The following monomer contents were determined by NMR measurements:
Isoprene 2.2 mol%
Isobutene 92.1 mol%
endo-vinylnorbomene I .7 mol%
Propene 15.4 +/- 0.5 mol%
Example 4 (comparative ~Y~ p'~) 200 g (3.57 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 300 g (7.128 mol) of propene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of -50~C
in an argon atmosphere. Polymerization took place according to the conditions ofExample 2. ~leld: 3.4 g = 0.7%.
15 The polymer was not investigated further because of the low yield. This example clearly shows the trend, which was already identifiable in Example 3, towards a reduction of the yield and Mooney value as the propene concentration increases.
Example 5 400 g (7.14 mol) of isobutene, 11.918 g (0.175 mol) of isoprene, 100 g (0.83 mol) of 5-vinyl-2-norbornene and 0.036 g (0.2 mmol) of anthracene were presented at a temperature of 40~C in an argon atmosphere. Polym~ri7~tion took place according to the conditions of Example 2. Yield: 53.7 g= 10.5%.
The slightly brown polymer obtained in this way had a gel content of 0.5% and an intrinsic viscosity of 0.391 dVg. Mv = 60,500.
The following monomer contents were determined by NMR measurements:
Isoprene 2.2 mol%
Isobutene 92.1 mol%
endo-vinylnorbomene I .7 mol%
Claims (14)
1. A terpolymer comprising an isoolefin with 4 to 16 carbon atoms, a conjugated diolefin with 4 to 6 carbon atoms and another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms with a molecular weight Mw of 50,000 to 2,000,000 g/mol, wherein the molar ratio adding up to 100 between the isoolefin and diolefin and unsaturated organic compound is 50-99:0.5-49.5:0.5-49.5.
2. A terpolymer according to claim 1, wherein the molecular weight Mw is from 100,000 to 1,000,000 g/mol.
3. A terpolymer according to claim 1 or 2, wherein said molar ratio is 60-98:1.5-20:0.5-20.
4. A terpolymer according to claim 1, 2 or 3, wherein the isoolefin is selected from isobutene, 2-methyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene and b-pinene, the conjugated diolefin is isoprene, butadiene, 2,3-dimethyl butadiene, cyclopentadiene, methylcyclopentadiene or 1,3-cyclohexadiene, and said another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms is ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene or 5-vinyl-2-norbornene.
5. A terpolymer according to claim 1, 2 or 3, wherein the isoolefin is selected from isobutene and 2-methyl-1-butene, the conjugated diolefin is isoprene, and said another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms is selected from ethene and propene.
6. A terpolymer according to any one of claims 1 to 5, wherein the terpolymer has a Mooney viscosity of 30 to 100, a gel content of 0% to 50% and an intrinsic viscosity of 0.5-2.
7. A terpolymer according to any one of claims 1 to 5, wherein the terpolymer has a Mooney viscosity of 45 to 80, a gel content of 0.5% to 5% and an intrinsic viscosity of 1-1.5.
8. A process for preparing a terpolymer according to claim 1, characterized in that an isoolefin with 4 to 16 carbon atoms, a conjugated diolefin with 4 to 6 carbon atoms and another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms are polymerized in the presence of an initiator system based on a vanadium tetrachloride/hydrocarbon solution, at a temperature of -100°C to +100°C and a pressure of 0.001 to 70 bars and wherein the molar ratio adding up to 100 between the isoolefin and diolefin and unsaturated organic compound is 50-99:0.5-49.5:0.5-49.5.
9. A process according to claim 8, wherein said molar ratio is 60-98:1.5-20:0.5-20.
10. A process according to claim 8 or 9, wherein the isoolefin is selected from isobutene, 2-methyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene and b-pinene, the conjugated diolefin is isoprene, butadiene, 2,3-dimethyl butadiene, 2,3-dimethylbutadiene, cyclopentadiene, methylcyclo-pentadiene or 1,3-cyclohexadiene, and said another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms is ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene or 5-vinyl-2-norbornene.
11. A process according to claim 8 or 9, wherein the isoolefin is selected from isobutene and 2-methyl-1-butene, the conjugated diolefin is isoprene, and said another singly or multiply unsaturated organic compound with 2 to 20 carbon atoms is selected from ethene and propene.
12. A process according to any one of claims 8 to 11, said initiator system further includes a co-initiator.
13. A use of a terpolymer according to any one of claims 1 to 7, to prepare a rubber vulcanizate.
14. A use of a terpolymer according to any one of claims 1 to 7, to prepare a tyre.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19718201.1 | 1997-04-30 | ||
| DE19718201A DE19718201A1 (en) | 1997-04-30 | 1997-04-30 | New terpolymers made from isoolefins, conjugated diolefins and mono- or polyunsaturated organic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2236010A1 true CA2236010A1 (en) | 1998-10-30 |
Family
ID=7828173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002236010A Abandoned CA2236010A1 (en) | 1997-04-30 | 1998-04-27 | New terpolymers of isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0875518A1 (en) |
| JP (1) | JPH10298241A (en) |
| KR (1) | KR19980081857A (en) |
| CN (1) | CN1198440A (en) |
| CA (1) | CA2236010A1 (en) |
| DE (1) | DE19718201A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10004048A1 (en) * | 2000-01-31 | 2001-08-02 | Bayer Ag | High molecular weight gel-free isobutene copolymers with high double bond contents |
| TWI229089B (en) * | 2000-12-12 | 2005-03-11 | Bayer Ag | Halogenated, high molecular weight, gel-free isobutene copolymers with elevated double bond contents |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3661870A (en) * | 1969-11-24 | 1972-05-09 | Goodyear Tire & Rubber | Isobutylene,1,3-butadiene,methyl butene copolymers |
| HU172849B (en) * | 1975-08-19 | 1978-12-28 | Muenyagipari Kutato Intezet | Process for preparing a copolymer from isobutylene and butadiene |
| DE2716877A1 (en) * | 1977-04-16 | 1978-10-26 | Veba Chemie Ag | PROCESS FOR MANUFACTURING HIGH-MELTING C DEEP 4 HYDROCARBON RESINS |
-
1997
- 1997-04-30 DE DE19718201A patent/DE19718201A1/en not_active Withdrawn
-
1998
- 1998-04-17 EP EP98107023A patent/EP0875518A1/en not_active Withdrawn
- 1998-04-24 JP JP10129773A patent/JPH10298241A/en active Pending
- 1998-04-27 CA CA002236010A patent/CA2236010A1/en not_active Abandoned
- 1998-04-30 CN CN98109733A patent/CN1198440A/en active Pending
- 1998-04-30 KR KR1019980015485A patent/KR19980081857A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0875518A1 (en) | 1998-11-04 |
| DE19718201A1 (en) | 1998-11-05 |
| JPH10298241A (en) | 1998-11-10 |
| CN1198440A (en) | 1998-11-11 |
| KR19980081857A (en) | 1998-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3560458A (en) | Process for polymerization of cationically polymerizable monomers | |
| US6015841A (en) | Initiator systems containing vanadium tetrachloride for the (co)polymerization of isoolefins | |
| US20090030169A1 (en) | Process for production of high-isoprene butyl rubber | |
| KR100893444B1 (en) | Halogenated, High Molecular Weight, Gel-Free Isobutene Copolymers with Elevated Double Bond Contents | |
| CA2236010A1 (en) | New terpolymers of isoolefins, conjugated diolefins and singly or multiply unsaturated organic compounds | |
| US3694377A (en) | Butyl rubber catalyst system | |
| US6846885B2 (en) | Process for the preparation of isoolefin copolymers | |
| CA2155497A1 (en) | Process for the production of polyisoolefins | |
| US20010014726A1 (en) | High molecular weight, gel-free isobutene copolymers with elevated double bond contents | |
| US3856763A (en) | Process for the preparation of high molecular weight, high unsaturation isobutylene-conjugated diene copolymers | |
| US3511821A (en) | Terpolymers of isobutylene-methylcyclopentadiene and a crosslinking agent | |
| US7202317B2 (en) | Polymerization of i-butene in hydrocarbon media using bis(borane) co-initiators | |
| US3436379A (en) | Process for the production of copolymers | |
| Van Lohuizen et al. | Cationic polymerization of some 1, 1‐dialkylethenes and methylenecycloalkanes | |
| EP1123326A1 (en) | Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof | |
| EP1215241B1 (en) | Process for the preparation of isobutene/isoprene copolymers | |
| MXPA97005110A (en) | New initiator system, containing vanadio, for the (co) dimerization of iso-olefi | |
| WO2004094481A2 (en) | Polymerization of i-butene in hydrocarbon media using bis(borane)co-initiators | |
| US6677421B2 (en) | Process for the preparation of isoolefin copolymers | |
| KR20070093847A (en) | Polymerization process using zinc halide initiators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |