KR100648642B1 - Radial Type Block Copolymer and A Method of the Production Thereof - Google Patents

Abstract

The present invention adds 10 wt% or less butadiene simultaneously with a polyvalent coupling agent to a diblock copolymer obtained by polymerizing an isoprene monomer after polymerization of a vinyl aromatic monomer using an anionic polymerization initiator, or proceeding with some coupling reaction after the addition of the polyvalent coupling agent. Simultaneously adding butadiene up to 10wt% to make a block copolymer of butadiene end and proceeding the coupling reaction at the same time, radial block air having both isoprene end and butadiene end in one molecule of coupling agent as shown in the following structural formula (1) It relates to a method for producing the coalescence.

(pS-pI) _n -X- (pB-pI-pS) _m

Where n, m> 1 (n + m) = 3

X = coupling agent -------------------> Formula (1)

The block copolymer is (1) 10-50 wt% vinyl aromatic polymer block, number average molecular weight 8,000-25,000, (2) 90-50 wt% isoprene polymer block, (3) 0-10 wt% butadiene polymer block (4) divalent The coupling rate 50-90% by the above coupling reaction, and (5) the number average molecular weights 80,000-400,000 of a polymer after coupling.

Block Copolymers, Couplings, Anionic Polymerization Initiators

Description

Radial Type Block Copolymer and A Method of the Production Thereof}

The present invention provides a partial coupling reaction by adding 10 wt% or less butadiene simultaneously with a polyvalent coupling agent or a 10 wt% or less butadiene after a polyvalent coupling agent is added to a diblock copolymer polymerized with isoprene monomer after polymerization of a vinyl aromatic monomer. The present invention relates to a method for producing a radial vinyl aromatic-conjugated diene-based block copolymer having both isoprene end and butadiene end in a single molecule coupling agent by simultaneously producing a block copolymer of butadiene terminal and advancing a coupling reaction. .

The present invention will be described in detail, by sequentially polymerizing vinyl aromatics and isoprene using an organic lithium initiator in an inert hydrocarbon solvent, and then simultaneously adding a coupling agent and butadiene, or by adding butadiene immediately after the coupling agent, Block copolymer of [vinyl aromatic polymer block]-[isoprene polymer block]-[vinyl aromatic polymer block] and [vinyl aromatic polymer block]-[obtained by some coupling reaction and the coupling reaction of butadiene end after addition of butadiene A block copolymer of isoprene polymer block]-[butadiene polymer block]-[isoprene polymer block]-[vinyl aromatic polymer block].

This method is achieved by the addition of a coupling agent and butadiene at the same time or by the addition of butadiene immediately after the coupling agent, thereby enabling the production of a radial vinyl aromatic-conjugated diene block copolymer having both isoprene and butadiene ends in one molecule of coupling agent. .

The present invention adds 10 wt% or less butadiene to the vinyl aromatic monomer and isoprene diblock copolymer at the same time as the polyvalent coupling agent, but immediately adds 10 wt% or less butadiene to the butadiene terminal while advancing butadiene below 10 wt%. The present invention relates to a method for producing a radial block copolymer having both isoprene end and butadiene end in one molecule of coupling agent by simultaneously producing a block copolymer of.

The block copolymers used for the adhesive and the adhesive are mainly vinyl aromatic and conjugated diene-based block copolymers, and conjugated diene monomers are used butadiene and isoprene depending on the purpose. Generally, a vinyl aromatic-conjugated diene block copolymer using butadiene is used for a hot melt adhesive, and a vinyl aromatic-conjugated diene block copolymer using isoprene is mainly used for an adhesive applied to a tape.

In addition, most of the vinyl aromatic and conjugated diene block copolymers used for the point-adhesives use a block copolymer having a structure in which a triblock copolymer and a diblock copolymer are mixed using a coupling method. On the other hand, the vinyl aromatic-isoprene block copolymer has shown that the coupling number is less than the actual number of possible coupling in the case of trivalent or higher polyvalent coupling due to the steric hindrance of the isoprene end.

Many researches have been done to solve this problem, and many research papers and patents have been published. Fetters and Hadjichristidis have reported the use of small amounts of butadiene in their research papers ( Macromolecules , 7 , 552, 1972 & 11 , 668, 1978) to reduce steric hindrance when coupling styrene and isoprene active anions. .

US Pat. Nos. 3,692,874 and 3,840,616 provide methods for increasing coupling efficiency by minimizing steric hindrance when coupling terminal anions of polystyrene polymers or polyisoprene polymers.

In addition, US Pat. Nos. 5,292,819 and 5,399,627 provide methods for adding less than 10% butadiene to the ends of isoprene blocks to increase the coupling efficiency of radial type vinyl aromatic-isoprene block copolymers using polyvalent coupling agents. Doing.

U.S. Patent Nos. 5,532,319 and 5,583,182 also suggest the use of butadiene in the preparation of radial type vinyl aromatic-isoprene block copolymers using polyvalent coupling agents. However, in this process, butadiene is added after isoprene polymerization and a coupling agent is added after butadiene polymerization for a predetermined time, and the end of the block copolymer coupled according to the amount of butadiene is fixed as isoprene or butadiene.

The present invention adds 10 wt% or less of butadiene to the vinyl aromatic monomer and isoprene diblock copolymer simultaneously with the polyvalent coupling agent, or 10 wt% or less of butadiene immediately after the addition of the polyvalent coupling agent, thereby advancing the butadiene terminal. The present invention relates to a method for producing a radial vinyl aromatic-conjugated diene-based block copolymer having both isoprene end and butadiene end in one molecule of coupling agent by advancing the coupling reaction.

The block copolymer at the isoprene end has a low coupling number at the beginning of the coupling reaction due to the steric hindrance of the isoprene end when the polyvalent coupling reaction proceeds. The coupling reaction easily occurs, and as the coupling reaction proceeds, the number of coupling increases.

That is, a radial vinyl aromatic-conjugated diene-based block copolymer in which both a block copolymer at the isoprene end and a block copolymer at the butadiene end are present in one coupling agent molecule is obtained.

Radial block copolymer production method of the present invention for achieving the above object,

Adding a vinylaromatic monomer in the presence of an organolithium initiator in an inert hydrocarbon solvent to polymerize until exhausted to synthesize a living polymer,

Adding isoprene monomer to the living polymer and polymerizing until exhausting to synthesize a diblock living polymer, and

A polyvalent coupling agent and butadiene are simultaneously added to the diblock living polymer to carry out a coupling reaction of some isoprene ends, butadiene polymerization reaction and coupling reaction of butadiene ends, or an additional butadiene monomer is added immediately after addition of the coupling agent. As the butadiene is exhausted, the coupling reaction is performed, and the coupling reaction between the butadiene terminal and the unreacted portion of the coupling agent is performed, and then the reaction is terminated.

The present invention will be described in more detail as follows.

The present invention adds butadiene of 10 wt% or less to the vinyl aromatic monomer and isoprene diblock copolymer simultaneously with the polyvalent coupling agent, or by adding 10 wt% or less of butadiene immediately after the addition of the polyvalent coupling agent, thereby proceeding with the coupling reaction of butadiene. The present invention relates to a method for producing a radial block copolymer having both isoprene and butadiene ends in one molecule coupling agent by making a terminal block copolymer and simultaneously carrying out a coupling reaction.

Referring to the polymerization step of the block copolymer of the present invention in detail, as a first step, a vinyl aromatic monomer and an organic lithium initiator are added under an inert hydrocarbon solvent to polymerize until exhausted ([vinylaromatic polymer] ] -Li).

In the present invention, as the vinyl aromatic monomer, one or more selected from styrene, α-methylstyrene, o -methylstyrene, p -methylstyrene, p - tert -butylstyrene, and 1,3-dimethylstyrene may be used. Most preferred is styrene.

In addition, as the inert hydrocarbon solvent for polymerization, it can be used by selecting from solvents commonly known for anionic polymerization. More specifically, cyclic aliphatic hydrocarbon solvents such as cyclohexane or cyclopentane, linear aliphatic hydrocarbon solvents such as n -hexane or n -heptane, and the like can be used. Preferably, cyclohexane, cyclohexane and n -hexane It is to use a mixture, a mixture of cyclohexane and n -heptane.

In addition, the organolithium initiator can be selected and used among those commonly used for anionic polymerization, and preferably n -butyllithium or sec -butyllithium is used.

In the second step, an isoprene monomer is added to the polymer and polymerized until exhausted to synthesize a vinylaromatic block-isoprene polymer block-Li type diblock living polymer ([vinylaromatic polymer]-[isoprene polymer] -Li ).

In the third step, a polyvalent coupling agent and butadiene are simultaneously added to the diblock copolymer to synthesize a triblock copolymer of some isoprene ends, but at the same time a butadiene polymerization reaction occurs, and a triblock copolymer is synthesized by a coupling reaction of butadiene ends. Alternatively, by adding butadiene after adding a polyvalent coupling agent, a coupling reaction of some isoprene ends occurs and simultaneously a butadiene polymerization and a coupling reaction with an unreacted portion of the coupling agent occur in the block copolymer polymer in which the coupling reaction is in progress. By carrying out the synthesis of the triblock copolymer, a block copolymer in which both isoprene end and butadiene end exist in one coupling agent molecule is produced.

In this case, as the coupling agent, halogenated alkanes such as 1,2-bis dichloromethylsilyl ethane, 1,2-bis trichlorosilyl ethane, trichloromethyltin, tetradrachlorotin, trifluoro phenyltin, A halogenated silicone such as trichloromethylsilane, tetrachlorosilane, trichloro phenylsilane, an aromatic compound such as divinylbenzene, and the like can be selected and used.

The temperature of each stage of the polymerization reaction can be the same or different temperature conditions, both constant temperature or adiabatic conditions. The range of possible reaction temperature is -10-150 degreeC, Preferably it is 10-100 degreeC.

The vinyl aromatic content of the triblock copolymer may be applied within 10 to 95%, but in order to maintain proper mechanical properties and application properties, the vinyl aromatic content is preferably 10 to 50% by weight, most preferably 10 to 35%. It is in the weight percent range.

The molecular weight of the vinyl aromatic block need not be a specific value, but in order to maintain mechanical properties and application properties, it is possible in the range of 5,000 to 40,000, preferably in the range of 8,000 to 20,000.

The molecular weight of the triblock copolymer can be in the range of 50,000 to 400,000, preferably 80,000 to 250,000.

Coupling ratios can be applied within 10 to 100%, but in order to maintain balanced physical properties, 30 to 100% is preferred, and the most preferred is 50 to 90%. The content of butadiene added together with the coupling agent after the isoprene polymerization or after the coupling agent is added may be 10 wt% or less, but less than 5 wt% is appropriate.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

Example 1.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 124.8 g of isoprene was added to carry out the polymerization reaction.

Three minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mole of silane tetrachloride and 3.2 g of butadiene were simultaneously added to conduct polymerization and coupling reactions simultaneously for 15 minutes. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

After coupling of the obtained block copolymer, the molecular weight and the number of couplings were analyzed by GPC over time, and the results are summarized in Table 1 below.

Example 2.

 After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 126.4 g of isoprene was added to carry out the polymerization reaction.

Three minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride and 1.6 g of butadiene were simultaneously added to perform polymerization and coupling reactions simultaneously for 15 minutes. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

After coupling of the obtained block copolymer, the molecular weight and the number of couplings were analyzed by GPC over time, and the results are summarized in Table 1 below.

Example 3.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 124.8 g of isoprene was added to carry out the polymerization reaction.

Three minutes after the isoprene polymerization temperature reached the highest temperature, 0.00045 mole of silane tetrachloride and 3.2 g of butadiene were simultaneously added to conduct polymerization and coupling reactions simultaneously for 15 minutes. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

After coupling of the obtained block copolymer, the molecular weight and the number of couplings were analyzed by GPC over time, and the results are summarized in Table 1 below.

Example 4.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2 L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium is added at 60 ° C to start the reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 126.4 g of isoprene was added to carry out the polymerization reaction.

Two minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride was added to carry out some coupling reaction. Two minutes after the addition of the silane tetrachloride, polymerization and coupling reactions were simultaneously performed for 15 minutes by adding 1.6 g of butadiene. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of couplings before and after butadiene injection of the obtained block copolymer were analyzed by GPC, and the results are summarized in Table 1 below.

Example 5.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 124.8 g of isoprene was added to carry out the polymerization reaction.

Two minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride was added to carry out some coupling reaction. One minute after the addition of the silane tetrachloride, polymerization and coupling reactions were simultaneously performed for 15 minutes by adding 3.2 g of butadiene. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of couplings before and after butadiene injection of the obtained block copolymer were analyzed by GPC, and the results are summarized in Table 1 below.

Example 6.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 126.4 g of isoprene was added to carry out the polymerization reaction.

Two minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride was added to carry out some coupling reaction. One minute after the addition of the silane tetrachloride, 1.6 g of butadiene was added to simultaneously carry out the polymerization and coupling reactions for 15 minutes. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of couplings before and after butadiene injection of the obtained block copolymer were analyzed by GPC, and the results are summarized in Table 1 below.

Example 7.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 124.8 g of isoprene was added to carry out the polymerization reaction.

Two minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride was added to carry out some coupling reaction. After 30 seconds of addition of silane tetrachloride, 3.2 g of butadiene was added to simultaneously carry out polymerization and coupling reactions for 15 minutes. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of couplings before and after butadiene injection of the obtained block copolymer were analyzed by GPC, and the results are summarized in Table 1 below.

Comparative Example 1.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 128 g of isoprene was added to carry out the polymerization reaction.

Three minutes after the isoprene polymerization temperature reached the highest temperature, 0.00055 mol of silane tetrachloride was added to carry out the coupling reaction. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of couplings of the obtained block copolymers after coupling were analyzed by GPC, and the results are summarized in Table 1 below.

Comparative Example 2.

After mixing 960 g of cyclohexane and 32 g of styrene in a 2L reactor under a nitrogen atmosphere, 0.0029 mol of n-butyllithium was added at 60 ° C to initiate a reaction. 10 minutes after the exothermic reaction reached the maximum temperature, 124.8 g of isoprene was added to carry out the polymerization reaction.

Three minutes after the isoprene polymerization temperature reached the highest temperature, 3.2 g of butadiene was added to carry out the polymerization reaction, and 0.00055 mol of tetrachloride tetrachloride was added to carry out the coupling reaction. A polymerization terminator was added to the polymerized living polymer solution, followed by stirring to completely remove the activity of the living polymer. An antioxidant was added to obtain a final product.

The molecular weight and the number of coupling were analyzed by GPC at the time after coupling of the obtained block copolymer, and the results are summarized in Table 1 below.

Example Comparative example One 2 3 4 5 6 7 One 2 Styrene (% by weight) 20 20 20 20 20 20 20 20 20 Isoprene (wt%) 78 79 78 79 78 79 78 80 78 Butadiene (wt%) 2 One 2 One 2 One 2 0 2 Catalyst (mmole) 0.0029 0.0029 0.0029 0.0029 0.0029 0.0029 0.0029 0.0029 0.0029 Coupling Agent (mmole) 0.00055 0.00055 0.00045 0.00055 0.00055 0.00055 0.00055 0.00055 0.00055 Butadiene Input Time The same time The same time The same time 2 minutes 1 minute 1 minute 30 seconds - - Molecular weight before coupling (Mp) 55,000 57,000 52,000 59,000 51,000 53,000 57,000 59,000 56,000 Molecular Weight After Coupling (Mp) 174,000 177,000 162,000 182,000 157,000 164,000 171,000 139,000 175,000 Coupling Rate (%) 71 74 55 72 72 76 75 75 73 Number of Couplings (Mp) 3.16 3.11 3.12 3.08 3.08 3.10 3.00 2.36 3.13

In the production of vinyl aromatic-isoprene block copolymers, the trivalent or higher polyvalent coupling may have a coupling reaction at the isoprene end, or a coupling number due to the steric hindrance of the isoprene anion end may be smaller than the actual possible coupling number. In order to solve the problem, the vinyl aromatic-conjugated diene-based block copolymer prepared by adding a small amount of butadiene to the end of the isoprene block is fixed to one type of isoprene or butadiene.

According to the present invention, the vinyl aromatic monomer and the isoprene diblock copolymer are added with 10 wt% or less butadiene simultaneously with the polyvalent coupling agent, or 10 wt% or less butadiene is added simultaneously with the partial coupling reaction after the polyvalent coupling agent is added. By making a block copolymer of butadiene terminal and proceeding the coupling reaction at the same time, a radial vinyl aromatic-conjugated diene-based block copolymer having both isoprene terminal and butadiene terminal in one molecule of coupling agent can be prepared.

Claims (15)

Using an organolithium initiator in an inert hydrocarbon solvent to add a vinylaromatic monomer to polymerize until exhausted to synthesize a living polymer, Adding isoprene monomer to the living polymer and polymerizing until exhausting to synthesize a diblock living polymer, and The triblock copolymer is synthesized by simultaneously adding trivalent or more coupling agent and butadiene to the diblock living polymer while synthesizing some isoprene-terminated triblock copolymer and synthesizing the triblock copolymer by butadiene-terminated coupling reaction, or After the addition of the polyvalent coupling agent, butadiene is added to cause the coupling reaction of some isoprene ends to occur, and at the same time, the butadiene polymerization and the coupling reaction with the unreacted portion of the coupling agent are carried out at the same time. Synthesizing the block copolymer to terminate the reaction, Method for producing a radial block copolymer having both isoprene end and butadiene end in one molecule coupling agent comprising a. The method of claim 1, wherein the inert hydrocarbon solvents include cyclohexane, cyclohexane and n - a mixture of hexane, cyclohexane and n - radial block process for producing a copolymer which is characterized by using one selected from a mixture of heptane. The method of claim 1, wherein n -butyllithium or sec -butyllithium is used as the organolithium initiator. The method of producing a radial block copolymer according to claim 1, wherein styrene is used as the vinyl aromatic monomer. The method of producing a radial block copolymer according to claim 1, wherein a coupling agent having a trivalent or higher functional group is used as the coupling agent. The method for producing a radial block copolymer according to claim 1, wherein the content of butadiene added is 10 wt% or less of the total weight of the vinyl aromatic monomer, isoprene, and butadiene. 7. The method for producing a radial block copolymer according to claim 6, wherein the content of butadiene added is 5 wt% or less of the total weight of the vinyl aromatic monomer, isoprene and butadiene. The method for producing a radial block copolymer according to claim 1 or 4, wherein the content of the vinyl aromatic monomer is 10 to 50% by weight of the total weight of the vinyl aromatic monomer, isoprene and butadiene. The method of claim 8, wherein the styrene content is 10 to 35% by weight of the total weight of styrene, isoprene and butadiene. The method for producing a radial block copolymer according to claim 1 or 4, wherein the molecular weight of the styrene block is in the range of 5,000 to 40,000. The method for producing a radial block copolymer according to claim 1, wherein the molecular weight of the block copolymer subjected to the coupling reaction is in the range of 50,000 to 400,000. The method for producing a radial block copolymer according to claim 11, wherein the molecular weight of the block copolymer is in the range of 80,000 to 250,000. The method of producing a radial block copolymer according to claim 1, wherein the coupling ratio of the coupling is in the range of 30 to 100%. The method of claim 13, wherein the coupling ratio is in the range of 50 to 90%. The method of claim 1, wherein the radial block copolymer has a isoprene end and a butadiene end in a single-molecule coupling system as shown in Formula 1 below. (pS-pI) _n -X- (pB-pI-pS) _m (Where n, m〉 1 (n + m) = 3 X = coupling agent)