GB2030993A – Preparation of Cis Polybutadiene
– Google Patents
GB2030993A – Preparation of Cis Polybutadiene
– Google Patents
Preparation of Cis Polybutadiene
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Publication number
GB2030993A
GB2030993A
GB7839998A
GB7839998A
GB2030993A
GB 2030993 A
GB2030993 A
GB 2030993A
GB 7839998 A
GB7839998 A
GB 7839998A
GB 7839998 A
GB7839998 A
GB 7839998A
GB 2030993 A
GB2030993 A
GB 2030993A
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United Kingdom
Prior art keywords
component
butadiene
nickel
polymerisation
polymer
Prior art date
1978-10-10
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GB7839998A
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GB2030993B
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ANOSOV V
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ANOSOV V
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1978-10-10
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1978-10-10
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1980-04-16
1978-10-10
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1978-10-10
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patent/GB2030993B/en
1980-04-16
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patent/GB2030993A/en
1982-09-22
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1982-09-22
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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
C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
C08F136/02—Homopolymers 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
C08F136/04—Homopolymers 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
C08F136/06—Butadiene
Abstract
Polymerisation of butadiene using as initiator system: (a) a nickel carboxylate or an organic complex of nickel; (b) an alkyl-, aryl-, alkoxy-, or aryloxyboron difluoride; and (c) an organometallic compound or hydride of a Group I, II or III metal (such as aluminium). The cis-1 ,4-content of the resulting polymer is high and there is little or no gel formation. The polymerisation is preferably effected in the presence of 0.01 to 5% (based on the weight of butadiene) of piperylene, whereby the freeze- resistance of the resulting polymer is increased.
Description
SPECIFICATION
Catalytic Polymerisation of Butadiene, to
Produce High Cis-1,4-polymer The present invention is concerned with a method of polymerising butadiene so as to produce a polymer containing a high proportion of the polymerised butadiene in the form of cis-1,4- units.
Many catalyst combinations for the polymerisation of butadiene in an organic solvent have been proposed. It is often desirable to produce polybutadiene containing a high proportion of cis-1,4-units; we have accordingly developed a catalyst system of good selectivity for the production of cis-1 ,4polybutadiene.
According to the invention, there is provided a method of catalytically polymerising butadiene in an organic solvent, in which there is used as the polymerisation catalyst a catalyst system comprising:
(a) a nickel carboxylate or an organic complex of nickel;
(b) an alkyl-, aryl-, alkoxy- or aryloxy-boron difluoride; and
(c) an organometallic compound or a metal hydride, the metal in the organometallic compound or hydride being of Group I, II or Ill of the Periodic Table of the Elements.
The method according to the invention is simple and involves little or no gel formation.
Oxygen and moisture should be excluded during polymerisation, since these have a detrimental effect on the activity of the catalyst system.
Component (a) should be soluble in the solvent used. Preferred examples of component (a) are nickel acety!-acetonate or nickel (ii) naphthenate and nickel (II) oleate; preferred examples of component (b) are methoxyborondifluoride, butoxyborondifluoride, n-hexylborondifluoride, npropoxyborondifluoride, phenylboron difluoride and phenoxyborondifluoride, and preferred examples of component (c) are triisobutyl aluminium, triethylaluminium and diisobutylaliminium hydride.
The molar ratio of component (a):component (b) is preferably 0.01-1:1; the molar ratio of component (a):component (c) is preferably 0.01.1 :1; and the molar ratio of component (b):component (c) is preferably 1-10:1.
The amount of component (a) used may vary over a wide range without significantly affecting the polymerisation rate; the molecular weight is affected, however.
The catalyst system may be prepared in various ways, for example, as follows:
1. Components (a) and (b) are mixed and then, after allowing the mixture to stand for a certain time, component (c) is added and the mixture stored for 5-10 minutes; or
2. Components (a) and (c) are mixed and allowed to stand for 10 minutes, then component (b) is added and the mixture is kept for 5-10 minutes.
The polymerisation of butadiene may, if desired, be carried out while mixing the catalyst components or, if desired, the system may be prepared in the presence of a monomer.
The catalyst preparation temperature is preferably in the range of –5 to 400C.
The polymerisation is preferably carried out in an autoclave, under an inert atmosphere, such as pure, dry argon, using an inert organic solvent, such as one or more hydrocarbons, which may be aliphatic, alicyclic or aromatic. An example of a suitable solvent is petroleum benzine. The volumetric ratio of solvent:butadiene is preferably 3 to 6:1.
Polymerisation is preferably carried out at a temperature of from 0 to 900C, more preferably 30 to 500C, for a polymerisation time of about 4 hours The resulting polymer may be stabilised and recovered conventionally, for example, using a vacuum drier at 80 to 100 C.
It is preferred that the polymerisation of butadiene in the method according to the invention is carried out in the presence of a minor amount of piperylene, preferably in an amount of 0.01 to 5%, based on the weight of butadiene, whereby the freeze-resistance of the resulting polymer is increased.
In order that the present invention may be more fully understood, the following examples are given by way of illustration only.
Example 1
Into an ampoule which was charged with dry, pure argon and at a temperature of -300C there were introduced 63 ml of petroleum benzine, 6 g of butadiene; 0.88 mi of a petroleum benzine solution of nickel naphthenate of concentration of 0.00096 g Ni/ml; 0.92 ml of a toluene solution ofmethoxyborondifluoride of concentration 0.014525 g/ml and 0.52 ml of a solution of triisobutylaluminium in petroleum benzine of concentration 0.936 g/ml. The molar ratios between the nickel-naphthenate (A) methoxyborondifluoride (B) and triisobutylaluminium (C) were as follows: A:B=0.08:1; A:C=0.16:1, B:C=2:1.
The ampoule was thermostatically controlled at a temperature of 400C, and polymerisation was allowed to take place for 4 hours. The resulting polymer was precipitated with alcohol and dried under vacuum at 80 to 1 000C to a constant weight.
The yield of polymer was 60% by weight and the intrinsic viscosity of the polymer was 2.51 6.
The polymer contained 97% cis-1 4-units, 2% trans-1,4-units and 1% vinyl groups.
Example 2
Example 1 was repeated, except that instead of the tri-isobutylaluminium solution there was used 1.04 ml of a 0.18 M solution of triethylalumimium.
The molar ratio of methoxyboron difluoride:triethylaluminium was 1:1 and the molar ratio of nickel naphthenate:triethylaluminium was 0.08:1.
The yield of polymer was 70% by weight and the intrinsic viscosity of the polymer was 1.803.
The polymer contained 97% cis-1,4-units.
Example 3
Example 1 was repeated, except that the catalyst system was replaced by the following: 0.8 ml of petroleum benzine solution of nickel oleate (A) of concentration 0.00106 g Ni/ml; 1.84 ml of a 0.18 M toluene solution of butoxyborondifluoride (B) and 0.52 ml of a 0.18
M solution of triethylaluminium (C). The molar ratios of the catalyst components were as follows:
A:B=0.1 :1; A:C=0.4:1; B:C=4:1.
The yield of polymer was 76% by weight and the intrinsic viscosity of the polymer was 1.449.
The polymer contained 95% cis-1,4-units, 3% trans-1,4units and 2% vinyl groups.
Example 4
Into a 3 litre autoclave provided with a stirrer and a jacket, there were charged 1,200 ml of petroleum benzine and 120 g of butadiene under an atmosphere of pure dry argon. Polymerisation was carried out for four hours in the presence of the following catalytic system: 35.6 ml of a petroleum benzine solution of nickel naphthenate (A) of concentration 0.96 g Ni/l; 29.2 ml of a toluene solution of n-hexylborondifluoride (B) of concentration 0.003436 g/ml and 10.3 ml of a petroleum benzine solution of triisobutylaluminium (C) of concentration 0.036 g/ml. The molar ratios of the components were as follows: A:B=0.031 :1; B:C=2.3:1; A:C=0.07:1.
After stopping and stabilisation, the polymer was isolated using live steam and dried on hot rolls; the polymer yield was 94.5% by weight as calculated for dry solids. The resulting polymer contained 97% cis-1,4-units; it contained no gel and has the following characteristics:
Mooney viscosity at 1 000C 49
Karrer plasticity 0.44
Cold flowability, mm/hr 11.3
Vulcanizates based on the polymer had the following properties:
vulcanization time, minutes 40
tensile strength, kgf/cm2 223
modulus at 300% elongation 83
resilience, % (rebound elasticity) 54
relative elongation,% 556.
Example 5
Polymerisation of butadiene was conducted as described in Example 4 hereinabove, except that as component B n-propoxyborondifluoride was used. The ratios of the components were as follows: A:B=0.09:1; B:C=3:1 A:C=0.27:1.
The yield of polymer was 100%, as calculated for dry solids; the Mooney viscosity was 48 and the freeze-resistance factor was 0.1.
Example 6
Example 4 was repeated, except that the catalyst system was replaced by 36.5 ml of a petroleum benzine solution of nickel naphthenate (A) of concentration 0.96 g Ni/l; 12.5 ml of a 0.3
M toluene solution of n-propoxyborodifluoride (B) and 98 ml of a 0.21 M solution of triisobutylaluminium (C). The molar ratios between the catalyst components were the same as in
Example 4. The polymerisation mixture also contained 26 ml of a toluene solution of transpiperylene of concentration of 92.5 g/l.
The yield of polybutadiene was 80% by weight; the resulting polybutadiene had a Mooney viscosity of 24.5 and a freeze-resistance factor of 0.3.
Example 7
Example 4 was repeated except that the catalyst system was replaced by 370.1 ml of a petroleum benzine solution of nickel naphthenate (A) of concentration of 0.94 g Ni/l, 25 ml of a 0.26 M solution of n-propoxyborondifluoride (B) and 3.3 ml of 0.04 M solution of triisobutylaluminium. The polymerisation mixture also contained 32 ml of a solution of transpiperylene in toluene with the concentration of 92.5 g/l.
The molar ratios between the components were as follows: A:B=1 :1; B:C=5:1 ; A:C=5:1.
The yield of polybutadiene was 80% by weight, the Mooney viscosity was 1 5 and the freezeresistance factor was 0.62.
Example 8
Into an ampoule filled with dry, pure argon at -400C there were added 65 ml of petroleum benzine and 6 g of butadiene. Polymerisation was carried out at 400C for 5 hours in the presence of the following catalyst system: 5.5 ml of a solution of nickel acetylacetonate (A) in petroleum benzine of concentration 0.05 g Ni/l; 2.32 ml of a toluene solution of methoxyborondifluoride (B) of concentration of 14.525 g/l and 1.05 ml of a solution of diisobutylaluminium hydride (C) of concentration of 9.0 g/l.
The molar ratios between the components were as follows: A:B=0.01 :1; B:C=1 0:1; A:C=0.1 :1. The polymer yield was 40% by weight and the percentage of cis-1,4-units in the polymer was 96.
Example 9
Into an ampoule filled with dry, pure argon at -50C there were added 65 ml of petroleum benzine, 0.88 ml of a petroleum benzine solution of nickel naphthenate (A) of concentration of 0.0163 moles per litre and 0.49 ml of a toluene solution of boron phenyldifluoride (B) of concentration of 0.26 moles per litre; the reaction
mixture was allowed to stand for 5 minutes. There were then added 1.04 ml of a petroleum benzine solution of triethylaluminium (C) of concentration of 0.09 moles per litre and the catalytic complex was kept for 10 minutes and the 6 g of butadiene were added; polymerisation was conducted at the temperature of 400C for 5 hours. The molar ratios of the components were as follows: A:B=0. 11:1; B:C=1.5:1; A:C=0.16:1.
The polymer yield was 78% by weight and the intrinsic viscosity of the polymer was 1.28. The polymer contained 97% cis-1,4-units.
Example 10
Into an ampoule filled with dry, pure argon at room temperature there were charged 65 ml of petroleum benzine, 0.88 ml of a petroleum benzine solution of nickel naphthenate (A) of concentration of 0.016 moles per litre and 1.04 ml of a petroleum benzine solution of triisobutylaluminium of concentration 0.18 moles per litre. The reaction mixture was allowed to stand for 10 minutes, whereafter there were added 2.04 ml of a toluene solution of phenoxyborondifluoride (C) of concentration 0.09 moles per litre. The final catalyst was kept for 5 minutes. The 6 g of butadiene were added and polymerisation was conducted at 300C for 4 hours. The molar ratios of the components were as follows: A:C=0.08:7; B:C=1 :1; A:B=0.08:7.
The yield of polybutadiene was 70% by weight and the intrinsic viscosity of the polymer was 1.01. The polymer contained 95% cis-1,4-units.
Claims (10)
Claims
1. A method of catalytically polymerising butadiene in an organic solvent, in which there is used as the polymerisation catalyst a catalyst system comprising:
(a) a nickel carboxylate or an organic complex of nickel;
(b) an alkyl-, aryl-, alkoxy- or aryloxy-boron difluoride; and
(c) an organometallic compound or a metal hydride, the metal in the organometallic compound or hydride being of Group I, II or Ill of the Periodic Table of the Elements.
2. A method according to claim 1, in which component (a) is nickel acetylacetonate, nickel naphthenate or nickel oleate.
3. A method according to claim 1 or 2, in which component (b) is methoxyborondifluoride, butoxyborondifluoride, n-hexylborondifluoride, npropoxyborondifluoride, phenylborondifluoride or phenoxyborodifluoride.
4. A method according to any of claims 1 to 3, in which component (c) is tri-isobutylaluminium, triethylaluminium or diisobutylaluminium hydride.
5. A method according to any of claims 1 to 4, in which the molar ratio of component (a):component (b) is 0.01 to 1:1;.
6. A method according to any of claims 1 to 5, in which the molar ratio of component (a):component (c) is 0.01 to 1:11.
7. A method according to any of claims 1 to 6, in which the molar ratio of component (b):component (c) is 1 to 10:1.
8. A method according to any of claims 1 to 7, in which butadiene is polymerised in the presence of piperylene in an amount of from 0.01 to 5%, based on the weight of butadiene.
9. A method of catalytically polymerising butadiene substantially as herein described in
Examples 1 to 10.
10. A polymer of butadiene, when prepared by a method according to any of claims 1 to 9.
GB7839998A
1978-10-10
1978-10-10
Preparation of cis polybutadiene
Expired
GB2030993B
(en)
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GB7839998A
GB2030993B
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1978-10-10
1978-10-10
Preparation of cis polybutadiene
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GB7839998A
GB2030993B
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1978-10-10
1978-10-10
Preparation of cis polybutadiene
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GB2030993A
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1980-04-16
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GB2030993B
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1982-09-22
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1978-10-10
1978-10-10
Preparation of cis polybutadiene
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1982-09-22
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1991-06-05
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Patent ceased through non-payment of renewal fee
