JPS6026016A - Block copolymer composition and its production - Google Patents

Abstract

PURPOSE:To obtain the titled composition of excellent mechanical strength and good processability, by polymerizing an aromatic vinyl compound in the pres- ence of an organolithium initiator, adding a nickel compound-BF3 compound catalyst system to the polymerization system and polymerizing 1,3-butadiene. CONSTITUTION:An aromatic vinyl compound or a mixture thereof with a conjugated diene compound is polymerized in the presence of an organolithium initiator to obtain first polymer blocks of a MW of 1,000-1,000,000. A nickel compound-BF3 compound catalyst system is added to this polymerization system, and 1,3-butadiene is polymerized. In this way, second polymer blocks comprising polybutadiene having a MW of 5,000-1,000,000 and a 1,4-bond content >=70% are formed. Preferred vinyl compounds include styrene and preferred conjugated diene compounds include butadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a block copolymer composition comprising an aromatic vinyl compound and butadiene, and more particularly to a block copolymer composition comprising a polybutadiene block having a high cis content and 71? The present invention relates to a block copolymer composition containing a block copolymer consisting of a styrene conductor block.

Conventionally, styrene was produced using an alkali metal as a gold catalyst.
Butadiene block copolymer, styrene-butadiene-
It is known to produce glazed block polymers of styrene block copolymers. However, regarding the microstructure of the polybutadiene moiety of these block polymers, 1,2 bonds account for 8% or more, cis 1,4-bonds account for 40% or less, and trans 1,4-bonds account for 52%. Only the following were obtained, and the results were not necessarily satisfactory in terms of mechanical strength and workability.

The purpose of the present invention is to take advantage of the characteristics of polybutadiene with a high cis content, to have a mechanical strength of 1 degree, and to have good processability.
An object of the present invention is to provide a block co-111 composition comprising polybutadiene and a polysnarene derivative.

Molecules obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and a conjugated diene compound according to the present invention [7] -@-1,000 to 1. (100, (1 (100) first polymer block (abbreviated as S) and 15.
000 to 1,000,000 second 1 combined block (
A block co-311 copolymer composition comprising an S-B type block copolymer consisting of a block copolymer (abbreviated as B) is provided.

The method for producing the block copolymer composition of the present invention includes, for example,
An aromatic vinyl compound or a mixture of the aromatic vinyl compound and a conjugated diene compound is combined in the presence of an organolithium initiator to form molecules [1,000 to 1,000,000
A first monopoly monopolymer block was obtained, and then a nickel compound-BF and a catalyst system of the compound were added to the polymerization system, and t and a butadiene were polymerized to obtain a polymer with a molecular weight of 5.000.
~1,000,000 and 70% cis 1,4-bonds 211, producing a second IF coalescing block consisting of the above polybutadiene.

In the present invention, the aromatic vinyl compound used for the first unitary block is represented by the general formula (wherein R1, i: H or CH3, Xt'i: H or argyl having 1 to 4 carbon atoms) Compounds that can be suitably used include styrene, p-methylstyrene, m-methylstyrene, and vinyltoluene.

Examples include pt-butylstyrene and p-etherstyrene, and one or more of these can be used. Among these, styrene is particularly preferred. In addition, the conjugated diene compound used is 1,3
-Butadiene, isogren.

Examples include 2,3-dimethylbutadiene and pentazene, and 181 or more of them can be used. Among these, butadiene is preferred. The first monomer block is 11 monomers of 1 aromatic vinyl compound, or a co-1 polymerizer of an aromatic vinyl compound and a conjugated diene compound, and the content of the aromatic vinyl compound is preferably 5 or more, preferably is 15] j'i% or more,
More preferably 25% by weight or more, particularly preferably: 40
Heavy weight: 1 or higher. The first polymer block is the first and! 82 polymer blocks total 1%/i1% or more of the total UK
2, preferably 3% by weight or more, and preferably 85% or less, more preferably 75111. 'fd% or less.

The second []1 coalescing block iJ, ], ]3-butadiene is a high-cis self-l-polybutadiene with synth 1
, 4 binding metal is 7011 mm or more, preferably 85% by weight
That's all.

The chain lengths of the first and second monomer blocks are not particularly limited, but the average molecular weight of the former is 1,000 to 1,000,
000 is appropriate, preferably 2,000 to 500,0
00. Furthermore, the impact is 3,000 to 250.0 (10
The molecular weight of the latter is (5)A.

5.000-1,000,000 is appropriate, preferably 10,000-750. Of, l O.

The content of the aromatic vinyl compound in the block conjugate silk composition of the present invention is 1% or more for serious injury in terms of impact, and more than 3% in favorable impact, and s51:%. The content is preferably 75% by weight or less, and more preferably 75% by weight or less. A yarn 11 composition having an aromatic vinyl compound content of 6038% or less is suitable for rubber applications, and a composition containing 60% by weight or more is suitable for resin applications.

The first 11 combined blocks are prepared under known polymerization conditions with an organolithium initiator. Examples of initiators include alkyl, aryl and cycloalkyl having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms.

Examples include organolithium compounds having an arylalkyl group. Preferred organolithium compounds include carbon atoms of 2 or more.
For example, n-butyllithium,
! 1ee-butyllithium, ethyllithium, styryllithium, etc. are used.

The amount of initiator can vary within a wide range, depending on the monomer glaze and desired molecular weight, but usually 0.5 to 500 mmol per 100 g of monomer is preferred.

As the polymerization solvent, one or more non-polar hydrocarbon solvents such as aliphatic, alicyclic and aromatic hydrocarbons are used. Preferably n-pentane, n-hexane, n-hebutane,
Cyclohexane, benzene.

Examples include toluene.

In the anionic polymerization of the first polymer block, it is preferable to sufficiently remove impurities such as moisture and alcohol from the system before introducing an on-machine additive that does not inactivate the anion center. The polymerization temperature is determined by the solvent
The temperature is usually -78'C or higher, preferably in the range of -50 to 100°C, although it is selected depending on the type of temperature.

The second polymer block is a nickel compound-11F added to the polymerization reaction bath solution containing the first polymer block.

It is obtained by adding a catalyst system of compounds and bringing them into contact with 1,3-butazoene monomer. Alternatively, the first polymer block may be added to a mixture of 1,3-tutadiene monomer, nickel compound-BF, and a compound catalyst for polymerization.

A particularly preferred order of addition is to add the 1,3-butadiene monomer to the first polymer block, add the nickel compound, and then add the BF5 compound.

Nickel naphthenate is a nickel compound.

Compounds soluble in solvents such as nickel octoate, nickel rosinate, and nickel stearate are preferred. Trifluoroborone may also be a complex with ether.

The amount of these nickel compounds and trifluorocarbons to be added is 1/20 to 5 times the molar amount, preferably 1/1, of the initiator used to form the first monomer block.
The amount is 0 to 3 times the molar amount. Polymerization is carried out batchwise or continuously.

The conjugate compositions of the present invention include a first polymer block (E3
) and a second monomer block (B), a polymer (B') consisting only of the second polymer block is included, and a polymer (B') consisting only of the second polymer block is included. Also included are those containing a polymer (B') consisting of.

The content of the S-B block combination in the composite composition of the present invention is usually 5% or more, preferably 1t to 15%! -% or more, preferably 30% or more by weight for use.

The combination of the present invention can be used alone, for example, natural rubber, polyisoprene, polybutadiene.

Styrene-butadiene copolymer, AkujJ mouth = ) I
Mix with a diene-based monomer such as a J-loopk diene copolymer, an acrylonitrile-isoprene copolymer, an olefin-based rubber-like monopolymer such as an ethylene-propylene copolymer, an egrene-propylene-diene copolymer, or an acrylic rubber, Can be used for various rubber applications such as various industrial rubber products and tires. Also, polystyrene, styrene-acrylonitrile copolymer.

Polyolefin, styrene-butadiene block polymer, styrene-isogrene block yJ? ') It can be applied to resin modification side with any resin.

Next, the present invention will be explained in more detail by showing examples. In addition, the measurement of the molecule l of the Pronk polymer of the present invention is carried out using Waters' high-speed GPC (Gruno J? It's hard to believe.

That is, the molecular weight of the styrene-containing block polymer is determined using a UV detector (245 nm), and the overall molecular weight is determined using an RI (refractometer). The microstructure of polybutadiene was determined by an infrared method (Morello method).

Example 1 In a 500 ml glass autoclave purged with nitrogen,
Cyclohexane 200+d and styrene 205"e were charged, the temperature was set to 0°C, and n-BuLi was injected at 2°72mM.

The mixture was colored yellow-orange, with the color of the steryl anion. Continuing to stir and react for 1 hour, the polymerization conversion rate was 100.
%It was confirmed. This polymer solution was placed in a 51-liter autoclave in advance with 2Kf of toluene and 1.3 kg under nitrogen.
- Charge butadier/3BOf and keep at 50℃ [Also inside, nickel naphthenate 0.82mM and BF3・OE
t 25.44 mM was injected. As a result of continued stirring,
51 The inside of the autoclave was colored pale yellow, and the reaction progressed. After reacting at 50°C for 4 hours, 2.6-dit was added to the reaction system.
A solution of -butyl-p-cresol 2i dissolved in methanol 51 was added to stop the reaction. Polymerization conversion rate is 95%
Met. The solvent was removed by a conventional method and dried with a roll at 120°C.

The resulting polymer was transparent and exhibited fluorescence due to the first polymer block. The molecule I determined from the GPC results of the entire polymer is 35 x 10', and the molecule L of the styrene block determined from the measurement results by the UV detector is 1.
2X10. Tg was 53°C.

The microstructure of the polybutadiene part is ale 114;9
0%.

Trans 1,4: 6%, 1.2 bond: 4%. 'rg was -117°C.

Comparative example, 1 Nippon Gosei Rubber Co., Ltd.'s Sisuriptadiene BRO2, polystyrene (Tobolex, MW, 70,000)
were roll blended at 5% 1 on a roll at 150°C for 30 minutes. The obtained polymer was a cloudy polymer.

Comparative Example, 2 In Example 1, the polymerization for the second polymer block was carried out without the addition of nickel compounds and borium compounds.

The polybutadiene portion of the resulting polymer was 41”
l cls -L42>'36% + ) 77 S1.475'5211.2- binding was 12%.

Examples 2 to 6 Polymers were obtained in the same manner as in Example 1 except that a 11 autoclave was used and the polymer composition of the first polymer block was changed as shown in Table 1.

The conjunctiva is summarized in Table-1. The microstructure of the polybutadiene portion of the second polymer was the same as in Example 1.

It was confirmed that when the first polymer block was a 'BD/ST copolymer, the styrene was shaped like a tapered block.

Table 1 shows the results of measuring the vulcanization physical properties of the polymer composition obtained as described above, which was blended according to the following formulation and vulcanized, based on JIS K6301.

[Composition]

Polymer 100 MU part Caden black (HAF) 50 ZnO 13 Stearic acid 2 Thiazole vulcanization accelerator (OBS) 1 Sulfur 1.5 Anti-aging agent 81ONA 1 Vulcanized at 145°C for 30 minutes.The physical properties are shown in Table 1. represents the physical properties of the above formulation, MV t'i - viscosity, Mwoo is the 300% modulus (Kff/crI), T is the tensile strength, Kt
t/ld), E8 represents elongation (%), H, and U hardness.

Claims (2)

[Claims] (1) Molecular weight 1,00 obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and a conjugated diene compound
Molecule i which is polybutadiene with a first polymer block (abbreviated as S) of 0 to 1,000,000 and an amount of cis 1,4-bonded gold of 70 or more 5,000 to 1.000
A block copolymer composition containing a 13-Bmfa block copolymer consisting of ,000 (0 m2 O:!Abbreviated as B). (2) Polymerize an aromatic vinyl compound or a mixture of the aromatic vinyl compound and a conjugated diene compound in the presence of an organolithium initiator to obtain molecules -fi: 1,000 to i, o.
A first polymer block of oo and ooo is obtained, and then a catalyst thread of a nickel compound-BF3 compound is added to the polymerization system, and 1,3-butadiene is polymerized to have a molecular weight of 5,000 to 1. , 000,000 and a cis-1,4-bound gold content of 70% or more.