JPS627203B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides improved multifunctional lithium-containing compounds suitable for initiation of polymerization in hydrocarbon media. The initiator of the present invention has a high degree of 1,4
- Promotes the polymerization of the 1,3-diene that gives rise to the addition and is soluble or readily made soluble in the amount of polymerization initiator in the hydrocarbon medium.

In particular, the initiator of the present invention has the formula (wherein R ₁ is hydrogen, an alkyl hydrocarbon group, a cycloalkyl hydrocarbon group, a cycloalkyl carbon group, an alkoxy group or an aromatic group, and R ₂ has at least 6 carbon atoms and is bonded to a lithium atom. is a divalent organic group having at least one aromatic ring directly attached to a carbon thereof, and may be an unspecified aprotic organic solvent soluble oligomer or polymer, and
R ₃ is an alkyl, cycloalkyl or aromatic group containing 1 to 20 carbon atoms. ) is a polyfunctional lithium-containing polymerization initiator compound.

R ₁ is preferably hydrogen. When R ₁ is other than hydrogen, it is a hydrocarbon group which may contain 1 to 16 carbon atoms and preferably has an aromatic ring or a tertiary carbon atom directly attached to an aromatic ring structure.

Preferably R ₂ contains 6 to 12 carbon atoms and most preferably 1,4-phenylene, 4,4-
Biphenylene or 4,4'-oxybisphenylene. R ₂ is carbon and hydrogen, and optionally oxygen,
Contains iron and/or sulfur. When oxygen and sulfur are present, they are present only in diphenyl oxide or diphenyl sulfide structures. Iron exists in the ferrocene structure.

R ₃ advantageously contains 2 to 20 carbon atoms and preferably 3 to 10 carbon atoms. The most preferred _R3 species is sec-butyl.

Similarly, liquid aliphatic, cycloaliphatic or aromatic hydrocarbon solutions or mixtures thereof in which the solution is a major part and a minor part of the formula (wherein R ₁ , R ₂ and R ₃ are as above, and
A lithium-containing catalyst comprising a multifunctional lithium-containing polymerization initiator compound in which R ₄ and R ₅ are each chemically bonded units of 1,3-butadiene or ituprene or mixtures thereof, and n+m is at least 20. Also within the scope of the invention are solutions which are particularly suitable for initiating the polymerization of vinyl group-containing compounds, especially vinyl hydrocarbon compounds, which are polymerizable in the presence of .

Similarly, the steps of the method are [R ₁ and R ₂ are as above and R 3 Li (R 3 is as above)] to give a compound of formula R ₃ Li (R ₃ is as above); (all substituents are as above) and subsequently contacting the resulting dispersion with at least one lithium polymerizable monomer to form a corresponding polymer. Also within the scope of the invention is a process for the polymerization of vinyl compounds containing at least one vinyl group and especially a vinyl hydrocarbon compound that is polymerizable in the presence of a lithium-containing catalyst, causing the polymerization of a vinyl hydrocarbon compound.

Compounds used here include the following:

4,4'-dibenzoyl-1,1'-biphenyl 4,4′-bis(1-phenylethenyl)-1,
1′-biphenyl (1,1'-biphenyl)-4,4'diylbis(3-methyl-1-phenylpentylidene)-bis(lithium) Oxydi-4,1-phenylenebis(3-methyl-1-phenylpentylidene)-bis(lithium) 4,4″-oxydibenzophenone Bis[4-(1-phenylethenyl)phenyl]ether 1,4-bis(1-phenylethenyl)benzene 1,4-phenylenebis(3-methyl-1-phenylpentylidene)bis(lithium) 4,4″-isoprolidene dibenzophenone 2,2-bis[4-(1-phenylethenyl)
Phenyl]propane (1-methylethylidene)bis-[4,1-phenylene(3-methyl-1-phenylpentylidene)]bis(lithium) The compounds according to the invention are easily prepared from compounds of the above type and are suitable for aromatic acids. It is easily synthesized by condensing chloride with aromatic compounds such as benzene, biphenyl, diphenyl ether, and the like in the presence of a Friedel-Crafts catalyst such as aluminum trichloride, in which the diketone has at least one aromatic Forms diketones with ketone groups separated by rings. This diketone compound is then subjected to a Wittich reaction that converts the getone group into a 1,1-vinylidene group. This divinylidene compound is then converted into an organolithium compound,
For example, contact with secondary butyllithium or tertiary butyllithium. The organolithium compound adds to the double bond to give the desired compound. The resulting dilithium compounds become soluble when contacted with small amounts of butadiene or isoprene in aliphatic, cycloaliphatic or aromatic hydrocarbon solvents such as hexane, cyclohexane or benzene. Generally dienes are used at 20% per mole of dilithium compound to make the compound soluble.
It is used in a ratio of 200 to 200 moles.

Example 1 A nitrogen purged reaction flask was charged with 23.4 grams of biphenyl dissolved in 50 milliliters of 1,2-dichloroethane. 85.5 g of benzoyl chloride and an additional 100 ml of 1,2-dichloroethane were added to the flask. The flask and contents were then cooled to about 10°C and 71.5g of aluminum trichloride was slowly added to the mixture with stirring. The solution turned dark red. The temperature of the reaction mixture was raised to 85°C over approximately 4 hours and held at this temperature for 17 hours. At the end of 17 hours, the reaction mixture was poured into ice water with stirring. The reaction mixture and ice water were then extracted with approx. 1 part of methylene chloride. The aqueous layer was discarded and the remaining mixture containing methylene chloride was washed with sodium bicarbonate solution and then with water. The methylene chloride solution was stirred with anhydrous sodium sulfate for 30 minutes, the mixture was filtered and the liquid was evaporated to dryness. The crude product obtained from drying the organic layer was then washed with methanol and subsequently with a 1:1 mixture of benzene and ethanol. This product was recrystallized from benzene.

17.6g of 4, with a melting point range of 217-218℃
4'-dibenzoyl-1,1'-biphenyl (compound) was obtained. Analysis of the product using infrared spectroscopy revealed a C
=O absorption was shown.

The compound was converted to 4,4'-bis(1-phenylethenyl)-1,1'-biphenyl (compound) by the following method.

10.6 mmol n as 0.53N benzene solution
-Butyllithium was dissolved in 50 milliliters of tetrahydrofuran in a nitrogen-purged glass reaction vessel.
4.06 g of methyltriphenylphosphonium bromide was mixed and the container was kept at ambient temperature (approximately 22° C.) for 2 hours. in 30ml of tetrahydrofuran
2.05g of compound suspension was added to the reaction mixture. The reaction vessel was kept at room temperature for approximately 16 hours. At the end of this time, the tetrahydrofuran was evaporated and the remaining solid was dissolved in a diethyl ether-water mixture in a 1:1 volume ratio. The water and ether were separated and the ether layer was washed with water and the ether was subsequently evaporated. The crude product compound was recrystallized twice from a 1:1 mixture of benzene and ethanol and washed with n-hexane to give a solid product, 4.
4'-bis(1-phenylethenyl)-1,1'-biphenyl (compound) had a melting point of 193-196°C. A benzene solution of the compound was prepared in a nitrogen-filled serum bottle equipped with a magnetic stirrer. This solution contained 0.5 g (1.41 mol) of compound and 70 milliliters of dry benzene. 7.2ml
Inject 0.482N, secondary butyl lithium n-hexane solution into the serum bottle using a hypodermic syringe.3.47
Milliequivalents of sec-butyllithium were obtained. The mixture was stirred at room temperature for 2 hours and 40 minutes and a deep blue dispersion was obtained.

The above treatment of the compound was repeated and a 15 mm portion of the resulting dispersion was withdrawn and poured into a serum bottle containing nitrogen and 0.05 ml of glacial acetic acid. The dispersed material dissolved and the color of the solution changed from deep blue to yellow. Lithium acetate formed in the solution and was then removed. The infrared spectrum of the remaining liquid showed complete disappearance of the absorption band at 900 cm ^-1 indicating that all vinyl groups had reacted with sec-butyllithium. The deep blue dispersion obtained by treatment of the compound, (1,1'-biphenyl)-4,
4'-diylbis(3-methyl-1-phenylpentylidene)-bis(lithium) was formed. Butadiene was polymerized using the compound in the following manner. A nitrogen purged reaction flask was charged with 850 mL of degassed dry benzene and the reaction mixture containing the compounds. Approximately 10 g of 1,3-butadiene monomer was added and the mixture was heated at room temperature for approximately 1 hour.
Stir for minutes. During this period, the dispersion became a solution. An additional 40 g of 1,3-butadiene was added and polymerization was carried out for about 40 minutes and the temperature of the reaction mixture was maintained at about 45-55°C. The reaction mixture was subsequently cooled to room temperature and 4 ml of distilled tetrahydrofuran were added with stirring. Once the tetrahydrofuran was uniformly dispersed, a solution of 2.44 milliequivalents of silicon tetrachloride in benzene was added. A visible gel formed immediately. After stirring for about 20 minutes, 1.5 ml of glacial acetic acid was added and the mixture containing gel was left overnight at room temperature. The resulting polybutadiene contained 40% ungelled polymer and 60% gel, but the above is by weight, confirming that the initiator compound was difunctional. The theoretical gel content was 86%.

For comparison, the above polymerization method was repeated except that sec-butyllithium was used as the catalyst instead of the compound. The recovered polybutadiene is
It was completely soluble in tetrahydrofuran, toluene and benzene. No gel was observed.

Example 2 The compound oxydi-4,1-phenylenebis(3-methyl-1-phenylpentylidene)-bis(lithium) was prepared in the following manner.

106.4 g of aluminum trichloride and 200 ml of methylene chloride were dissolved in a nitrogen-purged reaction vessel.
A solution of 91.94 g of benzoyl chloride was charged. The reaction vessel was cooled in an ice bath. A solution of 56 g diphenyl oxide and 20 ml methylene chloride was cooled to about 0°C and added to the reaction vessel. After 2 1/2 hours, the ice bath was removed and the container was allowed to warm to room temperature and was kept at ambient temperature for approximately 20 hours. After 20 hours, some of the methylene chloride had evaporated and was refilled. After an additional hour, the reaction mixture was poured onto ice. The resulting icy mixture was extracted twice with methylene chloride. The aqueous and organic layers were separated and the aqueous layer was removed. The organic layer was washed twice with a 10% by weight aqueous solution of potassium hydroxide. The aqueous layer was removed. The remaining organic layer was evaporated to dryness. The remaining crude product was dissolved in benzene and decolorized with charcoal. An equal volume of methanol was added to the decolorized benzene solution and 56.03 g of 4,4''-oxydibenzophenone (compound) was obtained in the form of white, crystalline flakes. -(1-Phenylethenyl)phenyl]ether (compound).Put 50ml into a nitrogen-purged serum bottle.
1.62 mmol of the compound dissolved in dry benzene was charged. 0.482Nsec. 8 ml of a hexane solution of butyl lithium was added to the Semla bolt using a syringe. A dark red dispersion of the compound in benzene was obtained. In another experiment, this dispersion was used in Example 1.
acidification using the method, and infrared spectral analysis
The absence of the 900 cm ^-1 band was shown, indicating the absence of vinyl groups. A nitrogen purged reaction flask was charged with 780 ml of degassed dry benzene and a dispersion containing 1.62 mmol of compound and 10 g of 1,3-butadiene. After about 90 minutes, the dispersion went into solution and an additional 60 g of 1,3-butadiene was added. The butadiene was polymerized for about 1 hour and 2 ml of tetrahydrofuran was added with stirring. When the tetrahydrofuran was uniformly dispersed, 2.09 meq of silicon tetrachloride in benzene was added.
After about 1 hour, 1 ml of glacial acetic acid was added. A visible gel formed when silicon tetrachloride was added.
Polybutadiene contained 56.6% gel. The theoretical amount of gel was calculated to be approximately 65%. The initiator was therefore difunctional.

In a nitrogen-purged flask, add 0.88 mmol of the compound dissolved in 25 ml of dry benzene and in addition 1.85 mmol dissolved in 4.3 ml of hexane with stirring.
Additional amounts of lithium were prepared by charging milliequivalents of sec-butyllithium. The compound began to form as a red dispersion in benzene. The dispersion was stirred for 3-1/2 hours at room temperature and
ml of isoprene was added to the dispersion. The dispersion was then heated to a temperature of about 60°C and after about 10 minutes the red dispersion turned into a reddish-brown solution. Add this solution to 450ml
40 g of butadiene dissolved in dry benzene was added to a nitrogen purged flask containing 40 g of butadiene dissolved in dry benzene. The reaction mixture was kept within the temperature range of 45-55°C. Polymerization of butadiene was completed in about 50 minutes. The reaction mixture was then cooled to about 35°C and 22ml of styrene was added.
The solution was stirred for about 2 minutes and 2 ml of distilled tetrahydrofuran was added. Reduce the temperature of the solution to about 35°C by about 1
Hold for an hour and add 0.15ml glacial acetic acid. The reaction mixture was diluted by addition of methanol which caused precipitation of the polymer formed. The precipitate was separated from the liquid and dried under vacuum at room temperature overnight. A portion of the polymer was compression molded with a test bar at a temperature of approximately 180°C. The polymer had a tensile strength at break of 3245 pounds per square inch (227 Kg/cm ² ) measured at 23°C and a mouth separation rate of 20 inches (50.8 cm)/minute. The elongation at break of the polymer sample was 1000%. The molecular weight of this polymer is determined by J.Applied Polym.Sci. 13 . 2359
(1969) by gel-permeation chromatography according to the method described in Runyon. Molecular weight is 123000 and 83000
It had a 20,000 butadiene center block and two 20,000 styrene end blocks.

Example 3 A reaction flask was purged with nitrogen and
58.5 g of aluminum trichloride and 160 ml of benzene were charged. A mixture of 40.6 g terephthaloyl chloride in 280 ml benzene was added to the reaction flask over 50 minutes from the bottom. The temperature of the reaction mixture was maintained at about 44-47°C for about 40 minutes and
The temperature rose to 68℃ in half an hour. The reaction vessel and contents were cooled in an ice water bath and the ice water was mixed with the reaction mixture. Methylene chloride was added and the aqueous and organic layers were separated. The organic layer was washed three times with aqueous sodium bicarbonate and twice with water. The organic layer was dried over anhydrous sodium sulfate. The particulate sodium sulfate was separated and the organic solvent was removed by evaporation. The resulting crude product remaining after evaporation was recrystallized from absolute alcohol containing about 0.5% benzene. 30 g of 1,4-dibenzoylbenzene having a melting point of 155-160°C was obtained. This 1,4-dibenzoylbenzene was then converted to 1,4-bis(1-phenylethenyl)benzene (compound) using the method set forth in Example 1 for converting compounds to compounds. A nitrogen purged flask was charged with 0.98 mmol of compound dissolved in 20 ml of dry benzene. Subsequently, 6 ml of 0.483Nsec-butyllithium-hexane solution was added. 2 of the mixture
Stir at room temperature for an hour. The mixture was a dark blue-red suspension and contained the compound 1,4-phenylenebis(3-methyl-1-phenylpentylidene)bis(lithium). A portion of the solution containing the compound was acidified with glacial acetic acid and the infrared spectrum showed no peak at 900 cm ^-1 indicating the absence of vinyl groups. Butadiene was polymerized using a dispersion containing the compound. A nitrogen purged reaction flask was charged with 450 ml of the dispersion containing benzene and the compound. 10g of 1,3-butadiene was added to the flask. The flask and contents were held at a temperature of about 40°C for about 30 minutes until the dispersion went into solution and 28 g of butadiene was added.
The contents of the flask were warmed to about 45-55°C for about 50 minutes. The reaction mixture and flask were then cooled to room temperature and 2 ml of distilled tetrahydrofuran was added with stirring. Subsequently, 1.12 meq of silicon tetrachloride in benzene was added. A gel appeared immediately. about 60
After a minute, 0.1 ml of glacial acetic acid was added. reaction mixture 30
Stir for a minute. The next day, the product was recovered by precipitation with the addition of methanol. This product is 55%
It contained a gel of Theoretical gel content is 67%;
This initiator was therefore difunctional.

Example 4 Using the same reaction conditions as shown in Example 1, 2,
A compound, 4,4''-isopropylidene dibenzophenone, was prepared from 2-diphenylpropane and benzoyl chloride.The amounts of the ingredients used were as follows: 2,2-diphenylpropane 20.8
g, benzoyl chloride 64.6 g, aluminum trichloride
61 g, and 160 ml of 1,2-dichloroethane. The diketone (compound) obtained was obtained as a viscous brown high boiling oil and showed one main peak on the gas chromatogram. Both infrared and nuclear magnetic resonance spectra showed the product to be the desired diketone. The above diketone (compound) is converted into a diolefin compound corresponding to the diketone, and 2,2-bis[4-(1-phenylethenyl)phenyl]propane (compound)
was subjected to a Wiiteizg reaction using the conditions given in Example 1 to obtain . The compound was obtained as a dark brown viscous oil. Both infrared and nuclear magnetic resonance spectra showed that the compound was obtained. Gas chromatographic testing showed this material to have a purity of over 90%. A nitrogen purged flask was charged with 2.15 mmol of compound dissolved in 20 ml of benzene. 12 ml of 0.482 Nsec.-butyllithium in hexane was added. All reactants were at room temperature. sec.- Upon addition of the butyl lithium solution, the color of the mixture changed to red and a suspended solid slowly formed. And the solution is compound XI, (1-methylethylidene)bis-
Contained [4,1-phenylene(3-methyl-1-phenylpentylidene)]bis(lithium). After stirring the reaction mixture at room temperature for 3 hours, it was used as a polymerization initiator as follows. That is, in a nitrogen flash reaction vessel, 500 ml of benzene,
A dispersion containing Compound XI and 10 g of 1,3-butadiene were charged. After about 1.5 hours, when the butadiene was added, the mixture was maintained at a temperature of about 45-50°C and cooled to room temperature after about 70 minutes. During cooling,
6.5 ml of distilled tetrahydrofuran was added. Upon completion of the tetrahydrofuran addition and brief stirring, 2.79 meq of silicon tetrachloride in benzene was added. Upon addition of silicon tetrachloride, a gel appeared immediately. The mixture was allowed to stand for approximately 20 minutes and 0.8ml of glacial acetic acid was added and the mixture was allowed to stand overnight. the next day,
The polymer was recovered by precipitation with methanol and the resulting product was found to contain more than 90% gel. The presence of gel indicated the bifunctionality of the initiator.

Example 5 Preparation of t-butylstyrene-styrene-t-butylstyrene triblock copolymer To a nitrogen-filled flask was added 450 ml of degassed dry benzene and 55 ml of purified styrene. Remove any residual impurities in the mixture until a pale yellow color appears.
-Butyllithium cyclohexane solution (0.56N)
It was removed by titration with A total of 0.31 milliequivalents of sec.-butyllithium was used. To this mixture were added 2 ml of purified tetrahydrofuran and 0.394 mmol of the compound as prepared in Example 2. The reaction mixture immediately turned deep orange-brown and began to generate heat. After 60 minutes the flask was cooled again. An additional 30 minutes was allowed to ensure all styrene monomer had reacted. 2.9 ml of purified t-butylstyrene was then added to the reaction flask containing the difunctional living polystyrene anion. Polymerization of t-butylstyrene was continued for an additional 60 minutes, after which a 0.5 ml portion of glacial acetic acid was added to terminate the living dianion. The polymer recovered by conventional precipitation and drying techniques was quantitative, indicating that all monomer added was used.

Example 6 Preparation of α,ω-dihydroxypolybutadiene Approximately 2 ml of ethylene oxide was condensed from a cylinder into a 50 ml glass bottle equipped with a high vacuum stopper and a rubber septum cap side arm. To this condensed ethylene oxide liquid, 4 drops of γ-butyllithium (1.5N in hexane) were added to react with any impurities present. A vial containing condensed ethylene oxide was then connected to the side arm of one reaction flask.

The reaction flask was then filled with N ₂ degassed dry benzene and about 25 g of purified butadiene monomer.
Residual impurities in the reaction mixture were removed by addition of 0.42 meq. of sec.-butyllithium in cyclohexane solution.

To this purified reaction mixture was added 0.56 mmol of the compound as prepared in Example 2. The reaction mixture was heated to 55°C. Polymerization continued at this temperature for approximately 60 minutes. At the end of the reaction period, remove the 55°C water bath and add 2 ml
of pure tetrahydrofuran was added. A decrease in viscosity was observed. After an additional 5 minutes of continuous stirring, the stopper connected to the condensed ethylene oxide vial and polymerization flask was opened. The dry ice-methylene chloride mixture used to condense ethylene oxide in the vial was similarly removed. A beaker of hot water was then used to accelerate the evaporation of ethylene oxide. The viscosity of the liquid in the polymerization flask increased rapidly and the light yellow color of the polybutadienyl dianion began to disappear. After about 4 minutes the color almost completely disappeared and the entire solution gelled. Stirring was stopped. The gel was allowed to stand for an additional 15 minutes, after which a 1 ml portion of glacial acetic acid was added. Upon addition of acetic acid, the gel structure immediately disappeared and the mixture became a liquid with normal viscosity. This generation and disappearance of gel grooves is caused by ⁺ Li ^- O due to ethylene oxide.
The cap reaction to produce the ˜O ⁻ Li ⁺ dianion was shown to be substantially complete and subsequent acidification produced the desired α,ω-dihydroxypolybutadiene.

The initiators according to the invention are easily prepared in situ by keeping a supply of the corresponding divinylidene compound. Divnylidene compounds are easily and rapidly converted to the corresponding lithium mixtures and are solubilized by the addition of small amounts of monomers such as butadiene. If desired, the entire system can avoid the addition of polar compounds such as ethers or amines, and thus 1,2 addition is minimized when polymerization of diene polymers is used, but when desired, 1,2
- Suitable polar compounds are added to increase the addition, increase the polymerization rate and reduce the viscosity of the reaction mixture.

Claims (1)

[Claims] 1 formula (R ₁ is hydrogen or a C ₁ to C ₁₆ alkyl hydrocarbon group,
is a cycloalkyl hydrocarbon group, an alkoxy group, or an aromatic group, and R ₂ is a dicyclic group having at least 6 carbon atoms and having at least one aromatic ring directly bonded to the carbon bonded to the lithium atom. and R ₃ is an alkyl, cycloalkyl or aromatic group containing from 1 to 20 carbon atoms) containing vinyl groups polymerizable in the presence of a lithium-containing initiator Polymerization initiator for compounds. 2 1,4-phenylenebis(3-methyl-1-
The compound according to item 1 above, which is phenylpentylidene)bis(lithium). 3. The compound according to item 1 above, which is (1,1'-biphenyl)-4,4'-diylbis(3-methyl-1-phenylpentylidene)bis(lithium). 4. The compound of item 1 above which is oxydi-4,1-phenylenebis(3-methyl-1-phenyl-pentylidene)bis(lithium). 5 (1-methylethylidene)bis-[4,1-
The compound according to item 1 above, which is phenylene(3-methyl-1-phenylpentylidene)]bis(lithium). 6 Formula of liquid aliphatic, alicyclic or aromatic hydrocarbon solvent or mixture thereof as major part and minor part (R ₁ is hydrogen or a C ₁ to C ₁₆ alkyl hydrocarbon group,
is a cycloalkyl hydrocarbon group, an alkoxy group, or an aromatic group, and R ₂ is a dicyclic group having at least 6 carbon atoms and having at least one aromatic ring directly bonded to the carbon bonded to the lithium atom. is a valent organic group and R ₃ is an alkyl, cycloalkyl or aromatic group containing 1 to 20 carbon atoms. ) and at least one of butadiene or isoprene chemically combined therewith, containing vinyl groups polymerizable in the presence of a lithium-containing initiator. Polymerization initiator solution of compound.