JPS6112712A - Block copolymer and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a block copolymer and a method for producing the same.

A first object of the present invention is to provide at least one conjugated diene D
A simple substance derived from at least one type of vinyl aromatic compound A, and at least one type of α-
Contains units derived from olefin M, and the structure has the formula: (
It is represented by Δ)c(D)b(M)C, and the day is 20 to 5
000, the above is within the range of 1 to 10, the above M is propylene, and the copolymerization degree of the propylene is 10.000 to 200, expressed as the number average molecular weight of block propylene. The object of the present invention is to provide a block copolymer, wherein the block polypropylene is comprised of a mixture of ictic, heterotactic, and syndiotactic triads.

The vinyl aromatic compound used in the present invention is
For example, styrene, α-methylstyrene, vinylnaphthalene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, methyl acrylate, ethyl acrylate,
Compounds capable of undergoing anionic polymerization reactions, such as methyl acrylate, ethyl methacrylate, or mixtures of these substances. The conjugated diene used is 1,3-
butadiene and substituted butadiene such as isoprene, piperylene, 2<3>-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, or mixtures of these substances.

According to a preferred embodiment of the invention, the block polypropylene of the block copolymer according to the invention is composed of a mixture of isotactic triad polymers, heterocuctic triad polymers and syndiocctic triad polymers.

The mixture generally contains 30-60% isotactic triad, 20-35% heterotactic triad and 20-35% syndiotactic triad.

A second object of the invention is to obtain α containing 3 to 12 carbon atoms.
- At least one monomer M selected from the group consisting of olefins and mixtures of ethylene and the α-olefin is added to a halogen of a transition metal Mt selected from the group consisting of titanium and vanadium in at least one solvent. compound and the formula '(A)-(D)=Li (A is at least one kind of vinyl aromatic compound, D is at least one kind of conjugated diene, and the atomic ratio L]/Mt is 1 to 3. An object of the present invention is to provide a process for producing a block copolymer in which the polymerization reaction is carried out in the presence of a catalyst system containing an organolitin polymer precursor of Polymer precursors and 4
is composed of a halide of a transition metal Mt having a valence of 20 to 5,000, the above is in the range of 1 to 10, and the concentration of the precursor in the reaction solvent is 2.
．． It is within the range of X10-3 to 5×10-3 mol/β.

The method according to the invention comprises: at a temperature in the range from 0° to +100°C and under a pressure in the range from about 0.8 to 1000 bar;
Moreover, it is possible to carry out in the presence of at least one hydrocarbon solvent.

Hydrocarbon solvents used in the process of the invention include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as hexane, benzene and the like, and fatty acids such as cyclopenkune, cyclohexane and methylcyclohexane. It is a cyclic hydrocarbon. These solvents are inert and can be used alone or as a mixture of two or more thereof. The amount of these hydrocarbon solvents used is generally 1 to 20 parts by weight based on 1 part by weight of all monomers. The solvent and monomer must be completely free of substances such as water, oxygen, carbon dioxide, some sulfur compounds, and acetylene before use. This is because said substances may destroy the (polymerization) initiator used in the method of the invention and the active ends of the growing polymer. According to another embodiment of the invention, by appropriate selection of the solvent and the order of addition of the monomers, it is equally possible to obtain block copolymers not only dissolved in the solvent, but also suspended. It is.

Among the transition metal halides included in the composition of the catalyst system according to the invention, titanium tetrachloride, vanadium tetrachloride and mixtures thereof are preferred.

On the other hand, the polymerization reaction time of monomer M is preferably in the range of 1 to 90 minutes, depending on the temperature and pressure selected.

Considering the respective reactivity of ethylene and α-olefins in the presence of the catalyst system, the mixture subjected to the polymerization reaction within the scope of the process of the invention contains at least 20 mol % of α-olefins. Preferably, it contains at most 80 mol% of ethylene.

The present invention will be specifically explained below using Examples.

However, the present invention is not limited in any way by the following examples.

Example 1 First, especially G, E, L, Reuvers (J, B,
L.

ROOVBR3) O, J: Hiess, Hiuta (
S, BYW8T iR) Njor, 7 riO%'L/4
Neil (Macromolecules).

By the well-known method described in 1975, 8.3,
An organolitin polymer precursor given by the following formula is prepared.

(Styrene),..., (Butadiene)3LiThe precursor was mixed with titanium tetrachloride in toluene in the molar ratio Li/T.
The reaction is carried out under conditions such that i is equal to 2. The organolitin precursor thus formed is then introduced into a glass reactor under an inert gas atmosphere. At the same time, the concentration of the precursor in the reaction solvent was increased to 6.5 x
Add an additional amount of toluene to give 10-3 moles/β.

Propylene is introduced into the reactor until the pressure reaches 850 mIJ bar. The polymerization reaction is carried out for 60 minutes at a constant temperature of 20 tons. At the end of the reaction, a bisequence copolymer of the formula:

(Styrene) Ioo (Butadiene) 3 (Propylene) c
The copolymer can be analyzed by the following method. ° One of them is Waters (WATBR3) GP
Gel permeation chromatography in 1,2,4-) dichlorobenzene at 140°C using a C200 apparatus;
“CN, M using 60 D, S, and 250 equipment
, R, spectroscopy.

The number average molecular weight of the polypropylene sequence, determined by the first method, is 30,500. FIG. 1 shows the spectrum obtained by the second method. This spectrum makes it possible to precisely identify the various blocks of the Visiken copolymer, with the polypropylene block containing 46% isotactic triads, 27% heterotactic triads and 27% syndiotactic triads. It is possible to determine that.

Example 2 Using the same catalyst system as in Example 1 containing 3 x 10-'' moles of precursor per 11, 80 mol% propylene and 20
Charge a gas mixture consisting of mol% ethylene. 2
A copolymerization reaction of these monomers is carried out under constant temperature conditions of 0° C. for 60 minutes. At the end of the reaction, the trisequence copolymer is recovered, which is analyzed using the same technique as in Example 1, with a yield of 665 g per hour, per atm and per g atom of titanium. Gel permeation chromatography spectra showed that the poly-(ethylene, cobropyrene) sequence had a number average molecular weight of 70,600 and that the sequence contained 50 mol% of units from ethylene and 50
It could be established that it contained mol % of units from propylene. FIG. 2 shows the 13CN, M, R, spectrum performed on the trisequence copolymer obtained.

[Brief explanation of the drawing]

Figure 1 shows the measurement results of CN, M, R, spectroscopy of the block copolymer obtained in Example 1, and Figure 2 shows the measurement results of the trisequence copolymer obtained in Example 2. It shows a measurement result similar to that of Patent applicant: Société Simitique des Charbonages, Niss, AR. Method of writing procedural amendments) July 25, 1985

Claims (10)

[Claims] (1) Contains a unit derived from at least one type of conjugated diene D, a unit derived from at least one type of vinyl aromatic compound A, and a unit derived from at least one type of α-olefin M, and has a structure is the formula (A)_a(D)_
A block copolymer represented by b(M)_c, wherein a is in the range of 20 to 5000 and b is in the range of 1 to 1.
0, the M is propylene, the copolymerization degree C of the propylene is in the range of 10,000 to 200,000 as a number average molecular weight of the block polypropylene, and the block polypropylene is an isotactic triad. , a mixture of heterotactic triads and syndiotactic triads. (2) The mixture constituting the block (M)_c is 30
Block copolymer according to claim 1, characterized in that it contains ~60% isotactic triad, 20-35% heterotactic triad, and 20-35% syndiotactic triad. (3) The vinyl aromatic compound is one selected from the group consisting of styrene, α-methylstyrene, vinylnaphthalene, vinyltoluene, and mixtures thereof. Block copolymer according to item 2. (4) The conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, and mixtures thereof. The block copolymer according to any one of claims 1 to 3, which is a seed. (5) At least one monomer M selected from the group consisting of an α-olefin containing 3 to 12 carbon atoms and a mixture of ethylene and the α-olefin is mixed with titanium in at least one solvent. a halide of a transition metal Mt selected from the group consisting of vanadium, and the formula: (A)_
a(D)_bLi (wherein A is at least one vinyl aromatic compound, D is at least one conjugated diene, and the atomic ratio Li/Mt is in the range of 1 to 3) A method for producing a block copolymer in which a polymerization reaction is carried out in the presence of a catalyst system containing a lithin polymer precursor and a halide of a tetravalent transition metal Mt, wherein the catalyst system is essentially a precursor of the organolithin polymer and a halide of a tetravalent transition metal Mt. wherein a is in the range of 20 to 5000, b is in the range of 1 to 10, and the concentration of the precursor in the reaction solvent is 2 x 10^-^3 to 5 x 10 ^-^2 mol/l
The method for producing the above block copolymer, characterized in that it is within the range of. (6) The method for producing a block copolymer according to claim 5, characterized in that the pressure of the reaction is in the range of 0.8 to 1000 bar. (7) The method for producing a block copolymer according to claim 5 or 6, wherein the reaction temperature is within a range of 0° to +100°C. (8) Production of the block copolymer according to any one of claims 5 to 7, wherein the solvent is selected from the group consisting of aliphatic, aromatic, and alicyclic hydrocarbons. Method. (9) The amount of the solvent is 1 to 20 parts by weight based on 1 part by weight of all monomers.
The method for producing a block copolymer according to any one of claims 5 to 8, characterized in that the block copolymer is used in a proportion of parts by weight. (10) The monomer M contains at least 20 mol% α-
Claims 5 to 5 are characterized in that they are mixtures containing olefins and at most 80 mol% ethylene.
9. A method for producing a block copolymer according to any one of Item 9.