CN102212196B - Coupled copolymer and preparation method thereof - Google Patents

Coupled copolymer and preparation method thereof Download PDF

Info

Publication number
CN102212196B
CN102212196B CN 201010156457 CN201010156457A CN102212196B CN 102212196 B CN102212196 B CN 102212196B CN 201010156457 CN201010156457 CN 201010156457 CN 201010156457 A CN201010156457 A CN 201010156457A CN 102212196 B CN102212196 B CN 102212196B
Authority
CN
China
Prior art keywords
silica
vinyl
hexenyl
pentenyl
propenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN 201010156457
Other languages
Chinese (zh)
Other versions
CN102212196A (en
Inventor
谢其诚
蔡智光
李彦贤
邱铭正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiwan Synthetic Rubber Corp
Original Assignee
Taiwan Synthetic Rubber Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiwan Synthetic Rubber Corp filed Critical Taiwan Synthetic Rubber Corp
Priority to CN 201010156457 priority Critical patent/CN102212196B/en
Publication of CN102212196A publication Critical patent/CN102212196A/en
Application granted granted Critical
Publication of CN102212196B publication Critical patent/CN102212196B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a coupled copolymer and a preparation method thereof. The coupled copolymer is prepared by reacting a copolymer obtained by polymerizing conjugated diene and a vinyl aromatic hydrocarbon monomer with an alkoxysilane coupling agent containing an alkenyl functional group; and a hydrogenated coupled copolymer can be obtained through a hydrogenation reaction. The coupling agent has a chemical formula shown as a formula (I), wherein R1 and R4 are same or different alkyl groups, R3 is an alkenyl-containing functional group, R5 is alkyl or alkenyl, and q is 1 or 0; when q is 0, k is equal to j which is 0, R2 is alkoxy, n is more than or equal to 1 and less than or equal to 3, m is more than or equal to 0 and less than or equal to 2, and the sum of m and n is 3; and when q is 1, the sum of k and j is 3, R2 is -(CH2)r-, r is 1 to 6, and the sum of m and n is 3. The coupling agent has high coupling efficiency; and the prepared coupling agent polymer has a four-arm polymer with higher content, so good rubber mechanical and physical properties can be provided.

Description

Coupled copolymer and manufacture method thereof
Technical field
The present invention relates to coupled copolymer and manufacture method thereof that a kind of manufacture is obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute, the multipolymer that the coupler by a novelty comes coupling to be obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute.More specifically, the present invention relates to the coupling of coupled copolymer and the hydrogenation of this coupling polymkeric substance, and containing the highly manufacture of the coupling polymkeric substance of coupling efficiency and high-content four arm ratios.
Background technology
Industrial normal use organic alkali metal compound is as the multipolymer of initiator polymerization of vinyl aromatic hydrocarbon and conjugated diolefine composition, and then utilize this base polymer of coupler coupling to form the multipolymer of linearity or hub-and-spoke configuration, but can prepare the heat plastics elastomer by this type of coupling polymerization, styrene-butadiene-styrene (Styrene-Butadiene-Styrene for example, SBS), styrene-isoprene-styrene copolymer-(Styrene-Isoprene-Styrene, SIS), and via making styrene-ethylene/butylene-styrene multipolymer (Styrene-Ethylene-Butene-Styrene after hydrogenation, SEBS), styrene-ethylene/propylene-styrene multipolymer (Styrene-Ethylene-Propylene-Styrene, SEPS).The coupling polymerization has many advantages, can comparatively properly control size and the lower viscosity of styrene block during as polymerization, compared with monomer polymerization method (Sequential Process) in proper order, the coupling polymerization also has satisfactory stability and higher efficiency when operation.
Yet, the coupler used for the past has problems, the disclosed coupler of English Patent 1014999 for example, this coupler contains the usefulness that halogenic ingredient can reduce antioxidant, use the polymer billet transparency of such coupler synthesized not good, the alkali metal halide by product of generation when carrying out coupling can cause pipeline corrosion, also can poison the growth of wastewater treatment mesophytization bacterium, adds this type of halogen-containing coupler and by multinational, listed in poisonous chemical substance and must not use.Therefore, the halogen composition coupler of some substituteds is developed gradually, R as disclosed as United States Patent (USP) 7220798 x-Si-(OR 1) ycoupler, and the disclosed Si of Taiwan patent 200307698 (OR) 4the organoalkoxysilane coupler.Yet, use the prepared multipolymer of this coupler, four arm polymer contents of gained are only 0 % by weight～5 % by weight, hydrogenation post polymerization thing causes processing because its four arms multipolymer content is lower after, product mechanical property modulus (modules) is less, rigidity is low, the stress can bear is also lower, in industrial application thereby limited to.
As mentioned above, although the existing known coupler of multiple prior art can be applicable to the multipolymer that polymerization is comprised of vinylaromatic hydrocarbon and conjugate diene monomer, the organoalkoxysilane coupler containing the alkenyl functional group that so the present invention researches and develops can solve the problem of above-mentioned coupler, use the not only Halogen compound by product generation of coupled copolymer of the organoalkoxysilane coupler institute polymerization containing the alkenyl functional group disclosed by the invention, its coupling efficiency reaches 60 % by weight～95 % by weight, its four arms polymer content can reach 10 % by weight～30 % by weight, via the hydrogenation coupled copolymer produced after hydrogenation, after its hydrogenation/front coupling efficiency and the four arm product content ratio of hydrogenation all can be higher than 0.7.As can be seen here, use the coupled copolymer of the organoalkoxysilane coupler institute polymerization containing the alkenyl functional group disclosed by the invention, no matter via hydrogenation whether, its four arms polymer content is all apparently higher than using the known organoalkoxysilane coupler of above-mentioned prior art, after its processing, product mechanical property modulus is larger, rigidity is high, and the stress can bear is also higher, in industrial application, can significantly promote.Organoalkoxysilane coupler containing the alkenyl functional group disclosed in this invention not only has high efficiency coupling efficiency, the good stability of prepared coupled copolymer, good rubber manufacturing machinery physical property still maintains certain coupling rate and four arm multipolymer ratios after over hydrogenation, therefore can be provided.
Summary of the invention
Purpose of the present invention is for being used a kind of organoalkoxysilane coupler containing the alkenyl functional group to prepare coupled copolymer.
The invention provides a kind of coupled copolymer, react and obtain with an organoalkoxysilane coupler containing the alkenyl functional group by the multipolymer obtained with vinyl aromatic hydrocarbon monomer institute polymerization by conjugated diolefine, wherein this organoalkoxysilane coupler that contains the alkenyl functional group is just like the chemical formula shown in formula (I):
Figure GSA00000080108600021
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
According to above-mentioned conception, the above-mentioned organoalkoxysilane coupler that should contain the alkenyl functional group, wherein R 1with R 4for identical or different C 1-4alkyl, R 3for C 2-4containing the alkenyl functional group, R 5for C 1-4alkyl or alkoxyl group, or C 2-4thiazolinyl, when q=0, R 2for C 1-4alkoxyl group.
According to above-mentioned conception, in the group that wherein this vinylaromatic hydrocarbon selects free vinylbenzene, alpha-methyl styrene, contraposition ethyl styrene, phenylcyclohexane ethene, contraposition vinyl toluene, ortho position vinyl toluene, a position vinyl toluene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene and above-mentioned composition to form.
According to above-mentioned conception, wherein this conjugated diolefine is selected free 1,3-butadiene, 2, and 3-dimethyl-1,3-butadiene, 3-butyl-1, in the group that 3-octadiene, isoprene, m-pentadiene, 2-phenyl-1,3-butadiene and above-mentioned composition form.
According to above-mentioned conception, wherein said coupled copolymer has 30,000～600,000 number average molecular weight.
According to above-mentioned conception, wherein the mol ratio of the consumption of this multipolymer and this coupler is 1.4～6.67.
According to above-mentioned conception, wherein should select free vinyltrimethoxy silane containing the organoalkoxysilane coupler of alkenyl functional group, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl three butoxy silanes, vinyl oxyethyl group bi-methoxy silane, the two propoxy-silane of vinyl oxyethyl group, the two butoxy silanes of vinyl oxyethyl group, the two (ethoxymethyl) TMOSs of vinyl, the two ethoxy-c TMOSs of vinyl, the two oxyethyl group butoxy silanes of vinyl, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, propenyl tripropoxy silane, propenyl three butoxy silanes, propenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of propenyl oxyethyl group, the two butoxy silanes of propenyl oxyethyl group, the two (ethoxymethyl) TMOSs of propenyl, the two ethoxy-c TMOSs of propenyl, the two oxyethyl group butoxy silanes of propenyl, the butenyl Trimethoxy silane, the butenyl triethoxyl silane, butenyl tripropoxy silane, butenyl three butoxy silanes, butenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of butenyl oxyethyl group, the two butoxy silanes of butenyl oxyethyl group, the two (ethoxymethyl) TMOSs of butenyl, the two ethoxy-c TMOSs of butenyl, the two oxyethyl group butoxy silanes of butenyl, the pentenyl Trimethoxy silane, the pentenyl triethoxyl silane, pentenyl tripropoxy silane, pentenyl three butoxy silanes, pentenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of pentenyl oxyethyl group, the two butoxy silanes of pentenyl oxyethyl group, the two (ethoxymethyl) TMOSs of pentenyl, the two ethoxy-c TMOSs of pentenyl, the two oxyethyl group butoxy silanes of pentenyl, the hexenyl Trimethoxy silane, the hexenyl triethoxyl silane, hexenyl tripropoxy silane, hexenyl three butoxy silanes, hexenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of hexenyl oxyethyl group, the two butoxy silanes of hexenyl oxyethyl group, the two (ethoxymethyl) TMOSs of hexenyl, the two ethoxy-c TMOSs of hexenyl, the two oxyethyl group butoxy silanes of hexenyl, two (vinyl-dimethyl oxygen base is silica-based) methane, two (vinyl-dimethyl oxygen base is silica-based) ethane, two (vinyl-dimethyl oxygen base is silica-based) propane, two (vinyl-dimethyl oxygen base is silica-based) butane, two (the vinyl diethoxy is silica-based) methane, two (the vinyl diethoxy is silica-based) ethane, two (the vinyl diethoxy is silica-based) propane, two (the vinyl diethoxy is silica-based) butane, two (the vinyl dipropoxy is silica-based) methane, two (the vinyl dipropoxy is silica-based) ethane, two (the vinyl dipropoxy is silica-based) propane, two (the vinyl dipropoxy is silica-based) butane, two (the vinyl dibutoxy is silica-based) methane, two (the vinyl dibutoxy is silica-based) ethane, two (the vinyl dibutoxy is silica-based) propane, two (the vinyl dibutoxy is silica-based) butane, two (the propenyl dimethoxy is silica-based) methane, two (the propenyl dimethoxy is silica-based) ethane, two (the propenyl dimethoxy is silica-based) propane, two (the propenyl dimethoxy is silica-based) butane, two (the propenyl diethoxy is silica-based) methane, two (the propenyl diethoxy is silica-based) ethane, two (the propenyl diethoxy is silica-based) propane, two (the propenyl diethoxy is silica-based) butane, two (the propenyl dipropoxy is silica-based) methane, two (the propenyl dipropoxy is silica-based) ethane, two (the propenyl dipropoxy is silica-based) propane, two (the propenyl dipropoxy is silica-based) butane, two (the propenyl dibutoxy is silica-based) methane, two (the propenyl dibutoxy is silica-based) ethane, two (the propenyl dibutoxy is silica-based) propane, two (the propenyl dibutoxy is silica-based) butane, two (the butenyl dimethoxy is silica-based) methane, two (the butenyl dimethoxy is silica-based) ethane, two (the butenyl dimethoxy is silica-based) propane, two (the butenyl dimethoxy is silica-based) butane, two (the butenyl diethoxy is silica-based) methane, two (the butenyl diethoxy is silica-based) ethane, two (the butenyl diethoxy is silica-based) propane, two (the butenyl diethoxy is silica-based) butane, two (the butenyl dipropoxy is silica-based) methane, two (the butenyl dipropoxy is silica-based) ethane, two (the butenyl dipropoxy is silica-based) propane, two (the butenyl dipropoxy is silica-based) butane, two (the butenyl dibutoxy is silica-based) methane, two (the butenyl dibutoxy is silica-based) ethane, two (the butenyl dibutoxy is silica-based) propane, two (the butenyl dibutoxy is silica-based) butane, two (the pentenyl dimethoxy is silica-based) methane, two (the pentenyl dimethoxy is silica-based) ethane, two (the pentenyl dimethoxy is silica-based) propane, two (the pentenyl dimethoxy is silica-based) butane, two (the pentenyl diethoxy is silica-based) methane, two (the pentenyl diethoxy is silica-based) ethane, two (the pentenyl diethoxy is silica-based) propane, two (the pentenyl diethoxy is silica-based) butane, two (the pentenyl dipropoxy is silica-based) methane, two (the pentenyl dipropoxy is silica-based) ethane, two (the pentenyl dipropoxy is silica-based) propane, two (the pentenyl dipropoxy is silica-based) butane, two (the pentenyl dibutoxy is silica-based) methane, two (the pentenyl dibutoxy is silica-based) ethane, two (the pentenyl dibutoxy is silica-based) propane, two (the pentenyl dibutoxy is silica-based) butane, two (the hexenyl dimethoxy is silica-based) methane, two (the hexenyl dimethoxy is silica-based) ethane, two (the hexenyl dimethoxy is silica-based) propane, two (the hexenyl dimethoxy is silica-based) butane, two (the hexenyl diethoxy is silica-based) methane, two (the hexenyl diethoxy is silica-based) ethane, two (the hexenyl diethoxy is silica-based) propane, two (the hexenyl diethoxy is silica-based) butane, two (the hexenyl dipropoxy is silica-based) methane, two (the hexenyl dipropoxy is silica-based) ethane, two (the hexenyl dipropoxy is silica-based) propane, two (the hexenyl dipropoxy is silica-based) butane, two (the hexenyl dibutoxy is silica-based) methane, two (the hexenyl dibutoxy is silica-based) ethane, two (the hexenyl dibutoxy is silica-based) propane, in the group that two (the hexenyl dibutoxy is silica-based) butane and derivative thereof form.
The present invention separately provides a kind of method of manufacturing coupled copolymer, and it comprises following steps: (a) multipolymer that comprises conjugated diolefine and vinyl aromatic hydrocarbon monomer of polymerization; (b) add this multipolymer to carry out coupled reaction the one organoalkoxysilane coupler containing the alkenyl functional group, form thus a coupled copolymer; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure GSA00000080108600041
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
According to above-mentioned conception, the above-mentioned organoalkoxysilane coupler that should contain the alkenyl functional group, wherein R 1with R 4for identical or different C 1-4alkyl, R 3for C 2-4containing the alkenyl functional group, R 5for C 1-4alkyl or alkoxyl group, or C 2-4thiazolinyl, when q=0, R 2for C 1-4alkoxyl group.According to above-mentioned conception, the coupling efficiency of this coupled copolymer of wherein said method is between 60 % by weight～95 % by weight.
According to above-mentioned conception, four arm multipolymer content of this coupled copolymer of wherein said method are between 10 % by weight～30 % by weight.
The present invention provides a kind of hydrogenation coupled copolymer again, and the multipolymer that this hydrogenation coupled copolymer is obtained with the vinyl aromatic hydrocarbon monomer polymerization by conjugated diolefine and an organoalkoxysilane coupler containing the alkenyl functional group react, then obtain via hydrogenation; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure GSA00000080108600051
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
According to above-mentioned conception, the above-mentioned organoalkoxysilane coupler that should contain the alkenyl functional group, wherein R 1with R 4for identical or different C 1-4alkyl, R 3for C 2-4containing the alkenyl functional group, R 5for C 1-4alkyl or alkoxyl group, or C 2-4thiazolinyl, when q=0, R 2for C 1-4alkoxyl group.According to above-mentioned conception, in the group that wherein this vinylaromatic hydrocarbon selects free vinylbenzene, alpha-methyl styrene, contraposition ethyl styrene, phenylcyclohexane ethene, contraposition vinyl toluene, ortho position vinyl toluene, a position vinyl toluene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene and above-mentioned composition to form.
As 12 described hydrogenation coupled copolymers of claim the, wherein this conjugated diolefine is selected free 1,3-butadiene, 2,3-dimethyl-1,3-divinyl, 3-butyl-1, in the group that 3-octadiene, isoprene, m-pentadiene, 2-phenyl-1,3-butadiene and above-mentioned composition form.
According to above-mentioned conception, wherein said hydrogenation coupled copolymer has 30,000～600,000 number average molecular weight.
According to above-mentioned conception, wherein the mol ratio of the consumption of this multipolymer and this coupler is 1.4～6.67.
According to above-mentioned conception, wherein should select free vinyltrimethoxy silane containing the organoalkoxysilane coupler of alkenyl functional group, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl three butoxy silanes, vinyl oxyethyl group bi-methoxy silane, the two propoxy-silane of vinyl oxyethyl group, the two butoxy silanes of vinyl oxyethyl group, the two (ethoxymethyl) TMOSs of vinyl, the two ethoxy-c TMOSs of vinyl, the two oxyethyl group butoxy silanes of vinyl, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, propenyl tripropoxy silane, propenyl three butoxy silanes, propenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of propenyl oxyethyl group, the two butoxy silanes of propenyl oxyethyl group, the two (ethoxymethyl) TMOSs of propenyl, the two ethoxy-c TMOSs of propenyl, the two oxyethyl group butoxy silanes of propenyl, the butenyl Trimethoxy silane, the butenyl triethoxyl silane, butenyl tripropoxy silane, butenyl three butoxy silanes, butenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of butenyl oxyethyl group, the two butoxy silanes of butenyl oxyethyl group, the two (ethoxymethyl) TMOSs of butenyl, the two ethoxy-c TMOSs of butenyl, the two oxyethyl group butoxy silanes of butenyl, the pentenyl Trimethoxy silane, the pentenyl triethoxyl silane, pentenyl tripropoxy silane, pentenyl three butoxy silanes, pentenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of pentenyl oxyethyl group, the two butoxy silanes of pentenyl oxyethyl group, the two (ethoxymethyl) TMOSs of pentenyl, the two ethoxy-c TMOSs of pentenyl, the two oxyethyl group butoxy silanes of pentenyl, the hexenyl Trimethoxy silane, the hexenyl triethoxyl silane, hexenyl tripropoxy silane, hexenyl three butoxy silanes, hexenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of hexenyl oxyethyl group, the two butoxy silanes of hexenyl oxyethyl group, the two (ethoxymethyl) TMOSs of hexenyl, the two ethoxy-c TMOSs of hexenyl, the two oxyethyl group butoxy silanes of hexenyl, two (vinyl-dimethyl oxygen base is silica-based) methane, two (vinyl-dimethyl oxygen base is silica-based) ethane, two (vinyl-dimethyl oxygen base is silica-based) propane, two (vinyl-dimethyl oxygen base is silica-based) butane, two (the vinyl diethoxy is silica-based) methane, two (the vinyl diethoxy is silica-based) ethane, two (the vinyl diethoxy is silica-based) propane, two (the vinyl diethoxy is silica-based) butane, two (the vinyl dipropoxy is silica-based) methane, two (the vinyl dipropoxy is silica-based) ethane, two (the vinyl dipropoxy is silica-based) propane, two (the vinyl dipropoxy is silica-based) butane, two (the vinyl dibutoxy is silica-based) methane, two (the vinyl dibutoxy is silica-based) ethane, two (the vinyl dibutoxy is silica-based) propane, two (the vinyl dibutoxy is silica-based) butane, two (the propenyl dimethoxy is silica-based) methane, two (the propenyl dimethoxy is silica-based) ethane, two (the propenyl dimethoxy is silica-based) propane, two (the propenyl dimethoxy is silica-based) butane, two (the propenyl diethoxy is silica-based) methane, two (the propenyl diethoxy is silica-based) ethane, two (the propenyl diethoxy is silica-based) propane, two (the propenyl diethoxy is silica-based) butane, two (the propenyl dipropoxy is silica-based) methane, two (the propenyl dipropoxy is silica-based) ethane, two (the propenyl dipropoxy is silica-based) propane, two (the propenyl dipropoxy is silica-based) butane, two (the propenyl dibutoxy is silica-based) methane, two (the propenyl dibutoxy is silica-based) ethane, two (the propenyl dibutoxy is silica-based) propane, two (the propenyl dibutoxy is silica-based) butane, two (the butenyl dimethoxy is silica-based) methane, two (the butenyl dimethoxy is silica-based) ethane, two (the butenyl dimethoxy is silica-based) propane, two (the butenyl dimethoxy is silica-based) butane, two (the butenyl diethoxy is silica-based) methane, two (the butenyl diethoxy is silica-based) ethane, two (the butenyl diethoxy is silica-based) propane, two (the butenyl diethoxy is silica-based) butane, two (the butenyl dipropoxy is silica-based) methane, two (the butenyl dipropoxy is silica-based) ethane, two (the butenyl dipropoxy is silica-based) propane, two (the butenyl dipropoxy is silica-based) butane, two (the butenyl dibutoxy is silica-based) methane, two (the butenyl dibutoxy is silica-based) ethane, two (the butenyl dibutoxy is silica-based) propane, two (the butenyl dibutoxy is silica-based) butane, two (the pentenyl dimethoxy is silica-based) methane, two (the pentenyl dimethoxy is silica-based) ethane, two (the pentenyl dimethoxy is silica-based) propane, two (the pentenyl dimethoxy is silica-based) butane, two (the pentenyl diethoxy is silica-based) methane, two (the pentenyl diethoxy is silica-based) ethane, two (the pentenyl diethoxy is silica-based) propane, two (the pentenyl diethoxy is silica-based) butane, two (the pentenyl dipropoxy is silica-based) methane, two (the pentenyl dipropoxy is silica-based) ethane, two (the pentenyl dipropoxy is silica-based) propane, two (the pentenyl dipropoxy is silica-based) butane, two (the pentenyl dibutoxy is silica-based) methane, two (the pentenyl dibutoxy is silica-based) ethane, two (the pentenyl dibutoxy is silica-based) propane, two (the pentenyl dibutoxy is silica-based) butane, two (the hexenyl dimethoxy is silica-based) methane, two (the hexenyl dimethoxy is silica-based) ethane, two (the hexenyl dimethoxy is silica-based) propane, two (the hexenyl dimethoxy is silica-based) butane, two (the hexenyl diethoxy is silica-based) methane, two (the hexenyl diethoxy is silica-based) ethane, two (the hexenyl diethoxy is silica-based) propane, two (the hexenyl diethoxy is silica-based) butane, two (the hexenyl dipropoxy is silica-based) methane, two (the hexenyl dipropoxy is silica-based) ethane, two (the hexenyl dipropoxy is silica-based) propane, two (the hexenyl dipropoxy is silica-based) butane, two (the hexenyl dibutoxy is silica-based) methane, two (the hexenyl dibutoxy is silica-based) ethane, two (the hexenyl dibutoxy is silica-based) propane, in the group that two (the hexenyl dibutoxy is silica-based) butane and derivative thereof form.
According to above-mentioned conception, wherein the hydrogenation ratio of this conjugated diene unit is higher than 50%, and vinylaromatic hydrocarbon unit hydrogenation ratio is lower than 10%.
According to above-mentioned conception, the ratio of the hydrogenation post polymerization thing coupling rate of wherein said hydrogenation coupled copolymer/hydrogenation prepolymer coupling rate and the ratio of hydrogenation post polymerization thing four arm product content/hydrogenation prepolymer four arm product content are greater than 0.7.
The present invention provides again a kind of method of manufacturing the hydrogenation coupled copolymer, and it comprises following steps: (a) polymerized conjugated diene and vinyl aromatic hydrocarbon monomer obtain a multipolymer; (b) add this multipolymer to carry out coupled reaction the one organoalkoxysilane coupler containing the alkenyl functional group, form thus a coupled copolymer; (c) this coupled copolymer of hydrogenation, form a hydrogenation coupled copolymer thus; Wherein should contain the chemical formula of the organoalkoxysilane coupler of alkenyl functional group just like formula (I):
Figure GSA00000080108600071
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
According to above-mentioned conception, the above-mentioned organoalkoxysilane coupler that should contain the alkenyl functional group, wherein R 1with R 4for identical or different C 1-4alkyl, R 3for C 2-4containing the alkenyl functional group, R 5for C 1-4alkyl or alkoxyl group, or C 2-4thiazolinyl, when q=0, R 2for C 1-4alkoxyl group.
According to above-mentioned conception, the coupling efficiency of this hydrogenation coupled copolymer of wherein said method is between 60 % by weight～95 % by weight.
According to above-mentioned conception, four arm multipolymer content of this hydrogenation coupled copolymer of wherein said method are between 10 % by weight～30 % by weight.
The accompanying drawing explanation
The schema that Fig. 1 is coupled copolymer manufacture method of the present invention.
The schema that Fig. 2 is hydrogenation coupled copolymer manufacture method of the present invention.
Wherein, 10,12,20,22,24 all mean reactions steps.
The polymer B that Fig. 3 produces for the polymer A coupler known with using prior art that uses coupler of the present invention and produce in the situation that the tension force do not refueled and amount of tension concern coordinate diagram.
The tension force of the polymer B that Fig. 4 produces for the polymer A coupler known with using prior art that uses coupler of the present invention and produce under the oil condition that doubles and amount of tension concern coordinate diagram.
Embodiment
The present invention will and coordinate accompanying drawing to be described in further detail by following preferred embodiment.
The coupled copolymer obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute provided by the present invention, by conjugated diolefine is reacted and obtained with an organoalkoxysilane coupler containing the alkenyl functional group with the multipolymer of vinyl aromatic hydrocarbon monomer institute polymerization, wherein this multipolymer optionally optionally can comprise at least one vinylaromatic hydrocarbon block A and at least one conjugated diene block B; This coupled copolymer can have the coupling efficiency between 60 % by weight～95 % by weight, and four arm multipolymer content of 10 % by weight～30 % by weight; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure GSA00000080108600081
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
According to above-mentioned conception, the above-mentioned organoalkoxysilane coupler that should contain the alkenyl functional group, wherein R 1with R 4for identical or different C 1-4alkyl, R 3for C 2-4containing the alkenyl functional group, R 5for C 1-4alkyl or alkoxyl group, or C 2-4thiazolinyl, when q=0, R 2for C 1-4alkoxyl group.Be applicable to the present invention obtains multipolymer vinylaromatic hydrocarbon to carry out polymerization and select in free vinylbenzene, alpha-methyl styrene, contraposition ethyl styrene, phenylcyclohexane ethene, contraposition vinyl toluene, ortho position vinyl toluene, a position vinyl toluene, group that the 1-vinyl-5-hexyl naphthalene, vinylnaphthalene and above-mentioned composition are formed, optimization styrene.
Be applicable to the present invention and obtain the conjugated diolefine choosing free 1 of multipolymer to carry out polymerization, 3-divinyl, 2,3-dimethyl-1,3-divinyl, 3-butyl-1,3-octadiene, isoprene, m-pentadiene, 2-phenyl-1, in the group that 3-divinyl and above-mentioned composition thereof form, preferred 1,3-butadiene, isoprene and composition thereof.
Vinyl aromatic hydrocarbon monomer of the present invention is preferably vinylbenzene, and conjugate diene monomer is preferably divinyl, isoprene; Wherein, vinylaromatic hydrocarbon block content accounts for approximately 5 % by weight～50 % by weight of above-mentioned multipolymer, is preferably 10 % by weight～45 % by weight.
Above-mentioned copolymer molecule chain optionally optionally can be the structure of A-B, A-B-B, B-A-B or A-B-A-B, and the B part is connected with coupler; Or the structure of B-A, A-B-A, B-A-B-A, the A part is connected with coupler, wherein A represents the vinylaromatic hydrocarbon block, be preferably polystyrene block, B is the block with rubber property, as the polymerized conjugated diene block, or the copolymer block of conjugated diolefine, also can be the block that conjugated diolefine and vinyl aromatic hydrocarbon monomer form, such polymkeric substance can have the characteristic of elastomerics and thermoplastically polymkeric substance concurrently.Therefore, this polymkeric substance can be used for manufacturing the standard operating procedure production of thermoplastically polymkeric substance, and its final product has elastomeric characteristic.
The control of the molecular weight of copolymer obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute is also an emphasis, be applicable to vinylaromatic hydrocarbon block A of the present invention and have 3,000～100,000 number average molecular weight, conjugated diene block B has 4,000～200,000 number average molecular weight, copolymer A-the B of vinylaromatic hydrocarbon and conjugate diene monomer has 7,000～300,000 number average molecular weight.Carry out by above-mentioned multipolymer and organoalkoxysilane coupler containing the alkenyl functional group disclosed in this invention the coupled copolymer that coupled reaction obtains and have 30,000～600,000 number average molecular weight, be preferably 70,000～500,000 number average molecular weight.Follow-up hydrogenation coupled copolymer after hydrogenation again has 30,000～600, and 000 number average molecular weight, be preferably 70,000～500,000 number average molecular weight.
The coupled copolymer that is applicable to the preferred specific embodiment of the present invention detailed disclosed reaction and step and obtain in the explanation of these polymkeric substance methods of following preparation.This analog copolymer can be produced by the technology of previously known, such as anionic polymerization, cationic polymerization, radical polymerization, complex body polymerization, solution polymerization process, emulsion polymerization method etc.Its method consists of two steps basically.Step 1 is to utilize organolithium compound to carry out polymerization to form a multipolymer with lithium terminal group to monomer; The multipolymer that step 2 is the lithium terminal group and coupler coupling defined above.Optionally can make hydrogenation coupling polymkeric substance via hydrogenation again.
The first step of present method is with the initial relevant monomer reaction of organolithium initiator, during polymerization, can carry out polymerization again and make molecular chain grow up to form the multipolymer with lithium terminal group after adding monomer, this polymerization procedure can be undertaken by one step or a series of consecutive steps.This polymer molecular chain can comprise single polymers, two kinds or more than the random disorderly row of two kinds of monomers or the multipolymer of cumulative block piecemeal, and this monomer can be simultaneously and the polymerization of organolithium initiator.When polymer molecular chain is comprised of the homopolymerization more than two or two or multipolymer, these indivedual segments can be by subsection charging monomer or continuous cumulative reinforced monomer mode produce piecemeal in proper order.
Being applicable to monomer of the present invention and preferred monomers defines in about the multipolymer obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute of the present invention aforementioned.
The organolithium initiator of the multipolymer obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute in order to preparation has the structure of R-Li usually, and wherein R is for containing C 1～C 12the alkyl of carbon atom.The object lesson that is applicable to organolithium initiator of the present invention comprises n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium etc., preferably n-Butyl Lithium, s-butyl lithium.The consumption of the organolithium initiator that polymerization is used depend on the molecular weight of the polymkeric substance that obtains of wish, the actual usage quantity of whole monomers of usually take is benchmark, its weight percent falls in 0.005 to 5 scope.
Polyreaction is carried out in the existence of solvent medium, and the solvent that this polymerization is used can be used continuously in hydrogenation thereafter.Be applicable to solvent in this polyreaction as inert organic solvents, it means the solvent that can not participate in reaction in polymerization and hydrogenation, this kind solvent comprises pentane, Skellysolve A, iso-pentane, 2, the aliphatic hydrocarbon of 2,4-trimethylpentane, isohexane, normal hexane, isoheptane, normal heptane, octane-iso, octane; Perhaps as the cycloparaffin series of hexanaphthene, methylcyclohexane, ethylcyclohexane, pentamethylene, suberane, methylcyclopentane; Perhaps arene compounds such as benzene,toluene,xylene, ethylbenzene, diethylbenzene and propyl benzene, the preferred hexanaphthene of the present invention and normal hexane.If use merely inert organic solvents as polymerisation medium in the situation that general, the rate of polymerization of vinylaromatic hydrocarbon or conjugated diolefine is slow and both polymerisation reactivity difference is quite large, now can overcome by the mode that adds polar solvent.The object lesson that is applicable to polar solvent of the present invention comprises the ether compounds such as tetrahydrofuran (THF), diethyl ether, ring amyl ether, dipropyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, glycol ether, dme, methyl ethyl ether, preferably tetrahydrofuran (THF) and diethyl ether.
The existence of polar solvent generally all can increase the content of vinyl (vinyl), and the scope that is applicable to vinyl of the present invention is 5～85%, can adjust its consumption according to the attribute of opposed polarity solvent its vinyl is fallen within this scope.
Polyreaction in step 1 occurs usually in several minutes to 8 hour scope, and comparatively ideal polymerization reaction time scope is in 20 minutes to 4 hours; As for polymerization temperature, usually in the scope of 0 ℃～200 ℃, preferable range is 50 ℃～120 ℃.
After treating polyreaction, start to carry out the second step coupled reaction, the lithium terminal group multipolymer namely polymerization obtained mixes with coupler.This step must just must be implemented before any material will stop polyreaction or remove adding of lithium atom from polymer molecular chain.Therefore the multipolymer obtained with vinyl aromatic hydrocarbon monomer institute polymerization by conjugated diolefine mixes with coupler, must be under the existence of these type of materials such as water, acid, alcohols just carries out before with the multipolymer that deactivates.
The usage quantity of coupler depends on the character of coupling efficiency and coupling polymkeric substance, the molar ratio of the consumption that desirable coupler consumption is this multipolymer and this coupler, this multipolymer Li/Si (moles/mole) with lithium base end of take is 1.4～6.67, and preferred proportion is 3.0～4.5.Use excessive coupler, Li/Si (moles/mole) ratio less than 1.4, can cause coupling efficiency to descend, and make coupling manner tend to low intensive copolymer products; If use the coupler of small amount, be that Li/Si (moles/mole) ratio surpasses 6.67, can make the much higher arm product of coupling manner trend intensity, but coupler content also can cause very little the time coupling efficiency to descend and the multi-arm product containing quantity not sufficient, so Li/Si (moles/mole) ratio preferably is controlled at 1.4～6.67 scope.
Be applicable to coupler of the present invention for the organoalkoxysilane coupler containing the alkenyl functional group, just like the chemical formula shown in aforementioned formula (I).The object lesson of coupling agent is vinyltrimethoxy silane (vinyl trimethoxy silane), VTES (vinyl triethoxy silane), vinyl tripropoxy silane (vinyl tripropoxy silane), vinyl three butoxy silanes (vinyl tributoxy silane), vinyl ethyoxyl bi-methoxy silane (vinyl ethoxy dimethoxysilane), the two propoxyl group silane (vinyl ethoxy dipropoxy silane) of vinyl ethyoxyl, the two butoxy silanes (vinyl ethoxy dibutoxy silane) of vinyl ethyoxyl, the two (ethoxymethyl) TMOSs (vinyl diethoxy methoxysilane) of vinyl, the two ethoxy-c TMOSs (vinyl diethoxy propoxy silane) of vinyl, the two ethyoxyl butoxy silanes (vinyl diethoxy butoxy silane) of vinyl, acrylic trimethoxy silane (propenyl trimethoxy silane), acrylic triethoxysilane (propenyl triethoxy silane), acrylic tripropoxy silane (propenyl tripropoxy silane), acrylic three butoxy silanes (propenyl tributoxy silane), acrylic ethyoxyl bi-methoxy silane (propenylethoxy dimethoxy silane), the two propoxyl group silane (propenyl ethoxy dipropoxy silane) of acrylic ethyoxyl, the two butoxy silanes (propenyl ethoxy dibutoxy silane) of acrylic ethyoxyl, the two (ethoxymethyl) TMOSs (propenyl diethoxy methoxy silane) of acrylic, the two ethoxy-c TMOSs (propenyl diethoxy propoxysilane) of acrylic, the two ethyoxyl butoxy silanes (propenyl diethoxy butoxy silane) of acrylic, cyclobutenyl trimethoxy silane (butenyl trimethoxy silane), cyclobutenyl triethoxysilane (butenyl triethoxy silane), cyclobutenyl tripropoxy silane (butenyl tripropoxy silane), cyclobutenyl three butoxy silanes (butenyl tributoxy silane), cyclobutenyl ethyoxyl bi-methoxy silane (butenyl ethoxy dimethoxy silane), the two propoxyl group silane (butenylethoxy dipropoxy silane) of cyclobutenyl ethyoxyl, the two butoxy silanes (butenyl ethoxy dibutoxy silane) of cyclobutenyl ethyoxyl, the two (ethoxymethyl) TMOSs (butenyl diethoxy methoxy silane) of cyclobutenyl, the two ethoxy-c TMOSs (butenyl diethoxy propoxy silane) of cyclobutenyl, the two ethyoxyl butoxy silanes (butenyl diethoxy butoxysilane) of cyclobutenyl, pentenyl trimethoxy silane (pentenyl trimethoxy silane), pentenyl triethoxysilane (pentenyltriethoxy silane), pentenyl tripropoxy silane (pentenyl tripropoxy silane), pentenyl three butoxy silanes (pentenyl tributoxy silane), pentenyl ethyoxyl bi-methoxy silane (pentenyl ethoxy dimethoxy silane), the two propoxyl group silane (pentenyl ethoxy dipropoxy silane) of pentenyl ethyoxyl, the two butoxy silanes (pentenyl ethoxy dibutoxy silane) of pentenyl ethyoxyl, the two (ethoxymethyl) TMOSs (pentenyl diethoxy methoxysilane) of pentenyl, the two ethoxy-c TMOSs (pentenyl diethoxy propoxy silane) of pentenyl, the two ethyoxyl butoxy silanes (pentenyl diethoxy butoxy silane) of pentenyl, hexenyl trimethoxy silane (hexenyl trimethoxy silane), hexenyl triethoxysilane (hexenyl triethoxy silane), hexenyl tripropoxy silane (hexenyl tripropoxysilane), hexenyl three butoxy silanes (hexenyl tributoxy silane), hexenyl ethyoxyl bi-methoxy silane (hexenylethoxy dimethoxy silane), the two propoxyl group silane (hexenyl ethoxy dipropoxy silane) of hexenyl ethyoxyl, the two butoxy silanes (hexenyl ethoxy dibutoxy silane) of hexenyl ethyoxyl, the two (ethoxymethyl) TMOSs (hexenyl dimethoxy methoxy silane) of hexenyl, the two ethoxy-c TMOSs (hexenyl dimethoxy propoxysilane) of hexenyl, the two ethyoxyl butoxy silanes (hexenyl dimethoxy butoxy silane) of hexenyl, two (vinyl-dimethyl oxygen base is silica-based) methane (bis (vinyl dimethoxy silyl) methane), two (vinyl-dimethyl oxygen base is silica-based) ethane (bis (vinyldimethoxy silyl) ethane), two (vinyl-dimethyl oxygen base is silica-based) propane (bis (vinyl dimethoxy silyl) propane), two (vinyl-dimethyl oxygen base is silica-based) butane (bis (vinyl dimethoxy silyl) butane), two (the vinyl diethoxy is silica-based) methane (bis (vinyl diethoxy silyl) methane), two (the vinyl diethoxy is silica-based) ethane (bis (vinyl diethoxysilyl) ethane), two (the vinyl diethoxy is silica-based) propane (bis (vinyl diethoxy silyl) propane), two (the vinyl diethoxy is silica-based) butane (bis (vinyl diethoxy silyl) butane), two (the vinyl dipropoxy is silica-based) methane (bis (vinyldipropoxy silyl) methane), two (the vinyl dipropoxy is silica-based) ethane (bis (vinyl dipropoxy silyl) ethane), two (the vinyl dipropoxy is silica-based) propane (bis (vinyl dipropoxy silyl) propane), two (the vinyl dipropoxy is silica-based) butane (bis (vinyl dipropoxy silyl) butane), two (the vinyl dibutoxy is silica-based) methane (bis (vinyl dibutoxysilyl) methane), two (the vinyl dibutoxy is silica-based) ethane (bis (vinyl dibutoxy silyl) ethane), two (the vinyl dibutoxy is silica-based) propane (bis (vinyl dibutoxy silyl) propane), two (the vinyl dibutoxy is silica-based) butane (bis (vinyldibutoxy silyl) butane), two (the acrylic dimethoxy is silica-based) methane (bis (propenyl dimethoxy silyl) methane), two (the acrylic dimethoxy is silica-based) ethane (bis (propenyl dimethoxy silyl) ethane), two (the acrylic dimethoxy is silica-based) propane (bis (propenyl dimethoxy silyl) propane), two (the acrylic dimethoxy is silica-based) butane (bis (propenyldimethoxy silyl) butane), two (the acrylic diethoxy is silica-based) methane (bis (propenyl diethoxy silyl) methane), two (the acrylic diethoxy is silica-based) ethane (bis (propenyl diethoxy silyl) ethane), two (the acrylic diethoxy is silica-based) propane (bis (propenyl diethoxy silyl) propane), two (the acrylic diethoxy is silica-based) butane (bis (propenyldiethoxy silyl) butane), two (the acrylic dipropoxy is silica-based) methane (bis (propenyl dipropoxy silyl) methane), two (the acrylic dipropoxy is silica-based) ethane (bis (propenyl dipropoxy silyl) ethane), two (the acrylic dipropoxy is silica-based) propane (bis (propenyl dipropoxy silyl) propane), two (the acrylic dipropoxy is silica-based) butane (bis (propenyldipropoxy silyl) butane), two (the acrylic dibutoxy is silica-based) methane (bis (propenyl dibutoxy silyl) methane), two (the acrylic dibutoxy is silica-based) ethane (bis (propenyl dibutoxy silyl) ethane), two (the acrylic dibutoxy is silica-based) propane (bis (propenyl dibutoxy silyl) propane), two (the acrylic dibutoxy is silica-based) butane (bis (propenyldibutoxy silyl) butane), two (the cyclobutenyl dimethoxy is silica-based) methane (bis (butenyl dimethoxy silyl) methane), two (the cyclobutenyl dimethoxy is silica-based) ethane (bis (butenyl dimethoxy silyl) ethane), two (the cyclobutenyl dimethoxy is silica-based) propane (bis (butenyl dimethoxy silyl) propane), two (the cyclobutenyl dimethoxy is silica-based) butane (bis (butenyldimethoxy silyl) butane), two (the cyclobutenyl diethoxy is silica-based) methane (bis (butenyl diethoxy silyl) methane), two (the cyclobutenyl diethoxy is silica-based) ethane (bis (butenyl diethoxy silyl) ethane), two (the cyclobutenyl diethoxy is silica-based) propane (bis (butenyl diethoxy silyl) propane), two (the cyclobutenyl diethoxy is silica-based) butane (bis (butenyl diethoxysilyl) butane), two (the cyclobutenyl dipropoxy is silica-based) methane (bis (butenyl dipropoxy silyl) methane), two (the cyclobutenyl dipropoxy is silica-based) ethane (bis (butenyl dipropoxy silyl) ethane), two (the cyclobutenyl dipropoxy is silica-based) propane (bis (butenyl dipropoxy silyl) propane), two (the cyclobutenyl dipropoxy is silica-based) butane (bis (butenyl dipropoxysilyl) butane), two (the cyclobutenyl dibutoxy is silica-based) methane (bis (butenyl dibutoxy silyl) methane), two (the cyclobutenyl dibutoxy is silica-based) ethane (bis (butenyl dibutoxy silyl) ethane), two (the cyclobutenyl dibutoxy is silica-based) propane (bis (butenyl dibutoxy silyl) propane), two (the cyclobutenyl dibutoxy is silica-based) butane (bis (butenyl dibutoxysilyl) butane), two (the pentenyl dimethoxy is silica-based) methane (bis (pentenyl dimethoxy silyl) methane), two (the pentenyl dimethoxy is silica-based) ethane (bis (pentenyl dimethoxy silyl) ethane), two (the pentenyl dimethoxy is silica-based) propane (bis (pentenyl dimethoxy silyl) propane), two (the pentenyl dimethoxy is silica-based) butane (bis (pentenyl dimethoxysilyl) butane), two (the pentenyl diethoxy is silica-based) methane (bis (pentenyl diethoxy silyl) methane), two (the pentenyl diethoxy is silica-based) ethane (bis (pentenyl diethoxy silyl) ethane), two (the pentenyl diethoxy is silica-based) propane (bis (pentenyl diethoxy silyl) propane), two (the pentenyl diethoxy is silica-based) butane (bis (pentenyl diethoxysilyl) butane), two (the pentenyl dipropoxy is silica-based) methane (bis (pentenyl dipropoxy silyl) methane), two (the pentenyl dipropoxy is silica-based) ethane (bis (pentenyl dipropoxy silyl) ethane), two (the pentenyl dipropoxy is silica-based) propane (bis (pentenyl dipropoxy silyl) propane), two (the pentenyl dipropoxy is silica-based) butane (bis (pentenyl dipropoxysilyl) butane), two (the pentenyl dibutoxy is silica-based) methane (bis (pentenyl dibutoxy silyl) methane), two (the pentenyl dibutoxy is silica-based) ethane (bis (pentenyl dibutoxy silyl) ethane), two (the pentenyl dibutoxy is silica-based) propane (bis (pentenyl dibutoxy silyl) propane), two (the pentenyl dibutoxy is silica-based) butane (bis (pentenyl dibutoxysilyl) butane), two (the hexenyl dimethoxy is silica-based) methane (bis (hexenyl dimethoxy silyl) methane), two (the hexenyl dimethoxy is silica-based) ethane (bis (hexenyl dimethoxy silyl) ethane), two (the hexenyl dimethoxy is silica-based) propane (bis (hexenyl dimethoxy silyl) propane), two (the hexenyl dimethoxy is silica-based) butane (bis (hexenyl dimethoxysilyl) butane), two (the hexenyl diethoxy is silica-based) methane (bis (hexenyl diethoxy silyl) methane), two (the hexenyl diethoxy is silica-based) ethane (bis (hexenyl diethoxy silyl) ethane), two (the hexenyl diethoxy is silica-based) propane (bis (hexenyl diethoxy silyl) propane), two (the hexenyl diethoxy is silica-based) butane (bis (hexenyl diethoxysilyl) butane), two (the hexenyl dipropoxy is silica-based) methane (bis (hexenyl dipropoxy silyl) methane), two (the hexenyl dipropoxy is silica-based) ethane (bis (hexenyl dipropoxy silyl) ethane), two (the hexenyl dipropoxy is silica-based) propane (bis (hexenyl dipropoxy silyl) propane), two (the hexenyl dipropoxy is silica-based) butane (bis (hexenyl dipropoxysilyl) butane), two (the hexenyl dibutoxy is silica-based) methane (bis (hexenyl dibutoxy silyl) methane), two (the hexenyl dibutoxy is silica-based) ethane (bis (hexenyl dibutoxy silyl) ethane), two (the hexenyl dibutoxy is silica-based) propane (bis (hexenyl dibutoxy silyl) propane), two (the hexenyl dibutoxy is silica-based) butane (bis (hexenyl dibutoxysilyl) butane) and derivative thereof etc., the substituting group of described its alkyl of derivative mainly can be C 5～C 12alkyl.
While carrying out coupled reaction, temperature can made adjustment in scope widely.Although the temperature of coupled reaction can be adjusted widely from 40 ℃～200 ℃, preferred scope maintains in the scope of 50 ℃～120 ℃.Coupled reaction usually by pure coupler or mixed coupling agent (coupler and solution phase are mixed) with single or add quantitatively multipolymer for several times and the mode that stirred can be implemented.The coupled reaction required time is quite of short duration, between the normal reaction period, greatly between 1 minute to 1 hour, but needs at low temperatures the reaction times of growing.Finally containing in the autoclave pressure of agitator, under the nitrogen sealing gland, the multipolymer that will be obtained with vinyl aromatic hydrocarbon monomer institute polymerization by conjugated diolefine reacts with various couplers, to prepare coupled copolymer.
The manufacture method of the coupled copolymer of the invention described above, can simplify the schema as Fig. 1.At first carry out step 10: multipolymer that comprises conjugated diolefine and vinyl aromatic hydrocarbon monomer of polymerization; Then carry out step 12: will add this multipolymer to carry out coupled reaction just like the organoalkoxysilane coupler containing the alkenyl functional group of formula (I) chemical formula, and form a coupled copolymer.Because the multipolymer of vinylaromatic hydrocarbon and conjugated diolefine contains the two keys of ethylenic unsaturation alkyl, the performances such as its thermotolerance, ultraviolet resistance, scale resistance, ozone resistance and weathering resistance are performed poor.After coupled reaction, although be recyclable coupled copolymer, but also can be optionally by the in addition optionally hydrogenation of the diene of this coupled copolymer part, significantly eliminate by hydrogenation the unsaturated double-bond that this analog copolymer includes, and then overcome the problems referred to above and its performance is obtained obviously and improve.In order to reach this purpose, any hydrogenation or method of selective hydrogenation that hydrogenation can be known via several these technology carry out, and for example use:
(1) organic acid salt of Co, Ni, Fe, Cr or acetylacetone based salt, alkoxyl group salt are reacted to Z-N (Ziegler-Natta) hydrogenation catalyst formed with the organoaluminum reductive agent, as United States Patent (USP) 3595942,3634549,3670054,3673281,3696088,3700633,3792127,3823203 etc.Aforesaid method all will be containing aromatics or the hydrogenation of ethylenic unsaturation alkyl double-bond polymerization thing with the catalyzer be applicable to, this type of catalyzer comprises VIII family metallic compound, and for example Ni or Co, be aided with suitable reductive agent, for example lithium, magnesium or aluminium hydride compounds, being applicable to reductive agent of the present invention is aluminum alkyls.The temperature range that this hydrogenation condition is 50 ℃～150 ℃, be preferably 70 ℃～120 ℃, and 10kg/cm 2～40kg/cm 2, be preferably 15kg/cm 2～30kg/cm 2pressure, complete reaction in aforesaid solvent.
(2) the hydrogenation Primary Catalysts (A) of cyclopentadiene (luxuriant) metal complexes (III, IV group 4 transition metal), being aided with organolithium, organic-magnesium, organic zinc or organoaluminum reductive agent is the formed hydrogenation catalyst of promotor (B), and being applicable to reductive agent of the present invention is organolithium or organoaluminum reducing catalyst.The temperature range that this hydrogenation condition is 50 ℃～180 ℃, be preferably 70 ℃～120 ℃, and 5kg/cm 2～40kg/cm 2, be preferably 10kg/cm 2～30kg/cm 2pressure, complete reaction in aforesaid solvent.
The hydrogenation of implementing according to aforesaid method must carry out under basic hydrogen, and hydrogen is preferably introduced in polymers soln with gaseous phase.
Can obtain at least 50% by above-mentioned method for hydrogenation, be preferably more than 90% hydropolymer, and in its hydrogenation process, be mainly the two keys in conjugated diene unit, as for the hydrogenation ratio of vinylaromatic hydrocarbon lower than 10%.When the multipolymer to vinylaromatic hydrocarbon and conjugated diolefine carries out hydrogenation, the two keys in its conjugated diene unit at least are hydrogenated 50%, are preferably more than 90%.
The manufacture method of the hydrogenation coupled copolymer of the invention described above, the schema that can simplify as Fig. 2 illustrates.At first carry out step 20: multipolymer that comprises conjugated diolefine and vinyl aromatic hydrocarbon monomer of polymerization; Then carry out step 22: will add this multipolymer to carry out coupled reaction just like the organoalkoxysilane coupler containing the alkenyl functional group of formula (I) chemical formula, and form a coupled copolymer; Finally carry out step 24: this coupled copolymer of hydrogenation forms a hydrogenation coupled copolymer.
The separation of hydrogenation post polymerization thing can be implemented by following method: the method that (1) hydrogenation post polymerization thing solution mixes with polar solvent, this kind solvent is poor solvent for hydrogenation post polymerization thing, as the similar solvent of acetone, alcohols, water or other tool same function, this kind solvent can precipitate hydrogenation post polymerization thing and be reclaimed; (2) hydrogenation post polymerization thing solution reclaims solvent and obtains hydrogenation post polymerization produce thing in the stripping mode; (3) in direct-fired mode, distill or solvent flashing and obtain hydrogenation post polymerization thing.
The hydride conversion rate of above-mentioned polymkeric substance can utilize infrared spectrometer to detect analysis, and relevant analytical procedure in this respect can be with reference to No. 4501857, United States Patent (USP).
Next, the prepared coupled copolymer of organoalkoxysilane coupler containing the alkenyl functional group disclosed in this invention will be used, and the coupled copolymer after hydrogenation carries out the analysis of coupling efficiency (Coupling Efficiency, CE).Coupling efficiency is defined as in the ratio that adds the multipolymer linked through coupler after coupler when coupled reaction finishes, the numerical value of coupling efficiency penetrates for the use gel coupling efficiency that chromatography (Gel Permeation Chromatography, GPC) data are calculated polymerisate in this implementation method.The account form of coupling efficiency is for the GPC area under a curve sum of all coupling species (two arms+tri-arms+tetra-arm multipolymers) has been added to beginning and end coupling polymer species area under a curve sum (linear single armed+bis-arms+tri-arms+tetra-arm multipolymers) divided by the GPC area under a curve of all couplings part, and this ratio is multiplied by 100 and coupling efficiency is changed into to percent value.Coupled copolymer disclosed in this invention has the coupling rate of 60 % by weight～95 % by weight, preferably the coupling efficiency of 65 % by weight～90 % by weight; Coupled copolymer after hydrogenation has the coupling rate of 60 % by weight～95 % by weight, preferably the coupling efficiency of 65 % by weight～90 % by weight.In addition, aspect multi-arm product content, coupled copolymer disclosed in this invention has four arm product content of 10 % by weight～30 % by weight, and the hydrogenation coupled copolymer has four arm product content of 10 % by weight～30 % by weight.
According to multipolymer and manufacture method and hydrogenation coupled copolymer and the manufacture method thereof obtained by conjugated diolefine and the polymerization of vinyl aromatic hydrocarbon monomer institute provided by the present invention, adopt coupler and multipolymer with good coupling effect to carry out coupled reaction.This coupler not only coupling efficiency is high, and can not produce the halogenide corroded pipeline in the coupling process, the four arm multipolymer content that produce after coupling can reach 10 % by weight～30 % by weight, can obtain 10 % by weight～30 % by weight after hydrogenation, apparently higher than 0 % by weight of using the known organoalkoxysilane coupler of prior art～5 % by weight four arm multipolymer content, mechanical property performance with the product after its processing of multipolymer of high four arm content is comparatively excellent, therefore in industrial application, can significantly promote.Another advantage be use disclosed in this invention containing the organoalkoxysilane coupler of alkenyl functional group the good stability of prepared coupled copolymer, good rubber manufacturing machinery physical property still can maintain certain coupling rate and four arm product content after over hydrogenation, therefore can be provided.
Below will be for several embodiment so that method of the present invention, feature and advantage to be described.Just conduct proof of these embodiment, and do not mean that restriction is anyways of the present invention, also not being used for limiting the scope of the invention, scope of the present invention should be take claim as foundation.
[embodiment 1-A, B, C, D, E]
The vinylbenzene of 20 g are dissolved in the hexanaphthene of 1000 g, add quantitative n-butyllithium solution, approximately 50 ℃ of starting temperatures, formal starting polymerization reaction after adding the tetrahydrofuran (THF) of 3.6 g.When whole styrene monomers approaches while reacting completely, add 78 g 1, the 3-butadiene solution is in mixed with polymers liquid, temperature rises to 65 ℃～70 ℃ (design of time described herein and temperature-visualized reactive tank, reactant species and reaction conditions etc. are done suitable adjustment), when almost reacting completely, whole 1,3-butadiene monomers completes the preparation of first step styrene/butadiene block copolymer.Extremely above-mentioned styrene/butadiene block copolymer is to carry out coupled reaction to add the quantitative organoalkoxysilane coupler containing the alkenyl functional group, and the mol ratio of initiator and coupler is about 3.0～4.5 in the present embodiment.In addition, coupler can once all add, and also can be divided into repeatedly and adding, and adding indegree is 1～4 time.After coupled reaction continues 30 minutes, carry out stripping in the stripping mode, now the molecular weight of dried polymkeric substance can be learnt, experimental result is as shown in table 1.The coupling efficiency ratio of coupling polymkeric substance is calculated and can be learnt by the analysis of GPC.
In embodiment 1-A, use vinyltrimethoxy silane as coupler, by experimental result table 1, found, use the prepared coupling polymkeric substance of vinyl-Trimethoxy silane, its coupling efficiency is 75.2 % by weight, four arm product content are 16.6 % by weight.
In embodiment 1-B, use vinyltriethoxysilane as coupler, by experimental result table 1, found, use the prepared coupling polymkeric substance of vinyl-triethoxyl silane, its coupling efficiency is 73.8 % by weight, four arm product content are 21.0 % by weight.
In embodiment 1-C, use the propenyl triethoxyl silane as coupler, by experimental result table 1, found, use the prepared coupling polymkeric substance of propenyl-triethoxyl silane, its coupling efficiency is 73.6 % by weight, four arm product content are 18.3 % by weight.
In embodiment 1-D, use the butenyl Trimethoxy silane as coupler, by experimental result table 1, found, use the prepared coupling polymkeric substance of butenyl-Trimethoxy silane, its coupling efficiency is 77.7 % by weight, four arm product content are 29.4 % by weight.
In embodiment 1-E, use vinyl oxyethyl group bi-methoxy silane as coupler, found by experimental result table 1, use the prepared coupling polymkeric substance of vinyl oxyethyl group bi-methoxy silane, its coupling efficiency is 76.5 % by weight, and four arm product content are 22.3 % by weight.
Table 1
Embodiment 1 Coupler Multipolymer weight average molecular weight (* 10 before coupling 4) Coupling rear copolymer weight average molecular weight (* 10 4) N-Butyl Lithium/coupler mol ratio Coupling efficiency (wt%) Four arm content (wt%) The hydrogenation situation
A Vinyltrimethoxy silane vinyl trimethoxy silane H 2C＝CH-Si-(OCH 3) 3 8.3 24.5 3.3 75.2 16.6 Hydrogenatable
B Vinyltriethoxysilane vinyl triethoxy silane H 2C＝CH-Si-(OC 2H 5) 3 7.7 24.0 3.3 73.8 21.0 Hydrogenatable
Figure GSA00000080108600181
[embodiment 2-A]
The hydrogenation of the present embodiment is selected Ni/Al hydrogenation catalyst system.Get 1100 g, the coupling polymkeric substance of embodiment 1-A and insert in the hydrogenation groove, process need completely cut off atmosphere, and temperature is increased to 80 ℃.Nickel octoate by quantitative 5% and 15% triethyl aluminum, mol ratio is 1: 2.5, ratio with 0.33phr and 0.27phr is mixed, and amounts to 0.6phr (unit weight of contained reagent in the monomer that phr is every 100 unit weights), with nitrogen, is pressed into the hydrogenation groove.Adjust hydrogen pressure and be set as 25kg/cm 2, make hydrogen slowly by the hydrogenation groove, to groove, press and equal setting pressure until reaction terminating.Determine the termination reaction time depending on the hydrogenation result, treat that polymer latex liquid is cooled to normal temperature and releases, remove catalyzer and reclaim polymkeric substance according to stripping under the exemplary steps of hydropolymer, the result after analyzing polymers hydrogenation, experimental result is as shown in table 2.The coupling polymkeric substance that experimental result is found embodiment 1-A thus is after the hydrogenation of Ni/Al catalyzer, after hydrogenation/and coupling efficiency before hydrogenation and four arm product content ratio are all higher than 0.7.
Table 2
Figure GSA00000080108600182
[embodiment 3-A]
The hydrogenation of the present embodiment is selected cyclopentadiene (luxuriant) metal complexes Ti/Al hydrogenation catalyst system.Get 1,000 g of the coupling polymerisate of embodiment 1-A and insert in the hydrogenation groove, process need completely cut off atmosphere, when hydrogenation groove temperature rises to 78 ℃, add dicyclic pentylene titanium dichloride and the triethyl aluminum of 100ppm, its molar ratio is 1: 2, and unlatching hydrogen, by pressure setting, be 25kg/cm 2.After hydrogenation to 60 minute, remove catalyzer and also according to stripping under the exemplary steps of hydropolymer, reclaim polymkeric substance, and sampling to carry out infrared spectrometer and detect and analyze to determine its hydrogenation ratio, experimental result is as shown in table 3.Experimental result finds that the coupling polymkeric substance of embodiment 1-A is after the hydrogenation of Ti/Al catalyzer thus, after hydrogenation/and the coupling efficiency before hydrogenation is with four arm product content ratio all higher than 0.7, and demonstration is via still maintaining certain coupling rate and four arm copolymer ratios after hydrogenation process.
Table 3
Figure GSA00000080108600191
[comparative example 1]
The vinylbenzene of 20 g are dissolved in the hexanaphthene of 1,000 g, add quantitative n-butyllithium solution, approximately 50 ℃ of starting temperatures, formal starting polymerization reaction after adding the tetrahydrofuran (THF) of 3.6 g.When whole styrene monomers approaches while reacting completely, add 78 g 1, the 3-butadiene solution is in mixed with polymers liquid, temperature rises to 65～70 ℃ (design of time described herein and temperature-visualized reactive tank, reactant species and reaction conditions etc. are done suitable adjustment), when almost reacting completely, whole 1,3-butadiene monomers completes the preparation of first step styrene/butadiene block copolymer.This segmented copolymer carries out coupled reaction from all kinds of different couplers, remaining step is carried out the stripping recovery according to the mode of embodiment 1, now the molecular weight of dried polymkeric substance can be learnt, and the coupling efficiency ratio of polymkeric substance is calculated and can be learnt by the analysis of GPC, carry out hydrogenation according to the described step of embodiment 2～3 again, the experimental result of different sorts coupler is as shown in table 4.
By experimental result table 4, found, using the triacetoxyl group methyl-monosilane in comparative example 1 is the prepared coupling polymkeric substance of coupler, its coupling efficiency is only 53.0 % by weight, four arm product content are only 6.5 % by weight, and it is invalid that use is carried out hydrogenation with the described Ti/Al hydrogenation catalyst of example 2A system.
[comparative example 2]
Repeat to carry out the preparation of coupling polymkeric substance as the experimental procedure of comparative example 1, this comparative example is used the methyl methoxy base silane as coupler.By experimental result table 4, found, in comparative example 2, use the prepared coupling polymkeric substance of methyl methoxy base silane, its coupling efficiency is 64.9 % by weight, and four arm product content are only 1.7 % by weight, and coupling efficiency and four arm product content are all not good.
[comparative example 3]
Repeat to carry out the preparation of coupling polymkeric substance as the experimental procedure of comparative example 1, this comparative example is used the two silane of six oxyethyl groups as coupler.By experimental result table 4, found, in comparative example 3, use the two prepared coupling polymkeric substance of silane of six oxyethyl groups, its coupling efficiency is 80.1 % by weight, still has suitable degree, but its four arms product content is only 4.0 % by weight, performance is coupler as disclosed in the present invention not, hence one can see that, even coupler has two coupling centers, can provide six coupling positions, also can't promote coupling efficiency and four arm product content.
[comparative example 4]
Repeat to carry out the preparation of coupling polymkeric substance as the experimental procedure of comparative example 1, this comparative example is used tetramethoxy-silicane as coupler.By experimental result table 4, found, in comparative example 4, use the prepared coupling polymkeric substance of tetramethoxy-silicane, its coupling efficiency is 75.3 % by weight, four arm product content are only 5.3 % by weight, under identical coupling condition, use the coupling polymkeric substance of tetramethoxy-silicane coupler can't obtain four high arm product content as using the coupling polymkeric substance prepared containing the organoalkoxysilane coupler of alkenyl functional group disclosed in this invention.
Table 4
Figure GSA00000080108600201
Figure GSA00000080108600211
[embodiment 4, comparative example 5]
The hydrogenation coupling polymkeric substance of table 5 for using vinyl disclosed in this invention-triethoxyl silane coupler to make, and the hydrogenation coupling polymkeric substance that uses the known coupler tetramethoxy-silicane of prior art the to make mechanical properties test experiments result of carrying out, do not refuel the tensile strength of coupling polymkeric substance and the oily coupling polymkeric substance after oil of doubling (oil product that uses of this experiment is that the Star-4 expansion of producing of U.S. Shell oil company is oily), elongation and modulus are as shown in table 5, the known prepared coupling polymer phase ratio of tetramethoxy-silicane coupler with using prior art, the coupling polymkeric substance that uses vinyl disclosed in this invention-triethoxyl silane coupler to make, no matter whether refuel larger modulus value, show that generally speaking it show when stretching more firm.
Table 5
In above-mentioned table 5 do not refuel and the oily situation that doubles under modulus value be shown in Fig. 3 and Fig. 4, wherein in embodiment 4, use coupler-vinyltriethoxysilane of the present invention, be denoted as coupler A, and use the known coupler-tetramethoxy-silicane of prior art in embodiment 5, be denoted as coupler B.Can know and find out from Fig. 3 and Fig. 4, use the modulus of the hydrogenation coupling polymkeric substance of coupler manufacturing of the present invention use prior art known the modulus of hydrogenation coupling polymkeric substance of coupler manufacturing obviously much higher.
In sum, can summarize following result with experiment of the present invention, the coupling polymkeric substance of embodiment 1A～E is for being used the organoalkoxysilane coupler containing the alkenyl functional group disclosed by the invention obtained, its coupling efficiency is 75.2,73.8,73.6,77.7,76.5 % by weight, and four arm product content are 16.6,21.0,18.3,29.4,22.3 % by weight; And comparative example 1～4 is the known made coupling polymkeric substance of coupler of use prior art, its coupling efficiency is 53.0,64.9,80.1,75.3 % by weight, and four arm product content are 6.5,1.7,4.0,5.3 % by weight.This experimental results show that the polymkeric substance with the organoalkoxysilane coupler manufacture containing the alkenyl functional group can obtain four arm products of high coupling efficiency and high-content, is the coupler stronger system more known than prior art.No matter in addition, use the polymkeric substance of manufacturing containing the organoalkoxysilane coupler of alkenyl functional group, be to carry out hydrogenation via Ni/Al hydrogenation catalyst or Ti/Al hydrogenation catalyst system, and its coupling efficiency and four arm product content all maintain at high proportion.Aspect measuring mechanical property, the coupling polymkeric substance that uses the vinyltriethoxysilane coupler to make, its tensile strength and modulus value are all higher than the made polymkeric substance of tetramethoxy-silicane, this experimental results show that the polymkeric substance that uses vinyltriethoxysilane disclosed by the invention to manufacture, the excellence that performance on the mechanical property tetramethoxy-silicane made polymkeric substance more known than prior art comes, therefore can provide good rubber manufacturing machinery physical property.
Although the present invention by preferred embodiment openly as above, it is not made an amendment without departing from the spirit and scope of the present invention and modifies in order to limit any technician who knows technique in this area.Therefore protection scope of the present invention should be with being as the criterion that claim was defined.Even person skilled in the art scholar does various modifications, but do not break away from the protection domain of claim.

Claims (16)

1. a coupled copolymer, it is at first to utilize organolithium compound to carry out to conjugated diolefine and vinyl aromatic hydrocarbon monomer the multipolymer that polymerization obtains having the lithium terminal group, then the multipolymer and that has the lithium terminal group by this is containing the organoalkoxysilane coupler of alkenyl functional group 1.4～6.67 obtain with quantitative response in molar ratio, it is characterized in that, four arm multipolymer content of described coupled copolymer are between 10 % by weight～30 % by weight; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure FDA00002281528400011
Formula (I)
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
2. coupled copolymer as claimed in claim 1, it is characterized in that, described vinylaromatic hydrocarbon is selected from vinylbenzene, alpha-methyl styrene, contraposition ethyl styrene, phenylcyclohexane ethene, contraposition vinyl toluene, ortho position vinyl toluene, a position vinyl toluene, 1-vinyl-5-hexyl naphthalene and vinylnaphthalene.
3. coupled copolymer as claimed in claim 1, is characterized in that, described conjugated diolefine is selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, isoprene, m-pentadiene and 2-phenyl-1,3-butadiene.
4. coupled copolymer as claimed in claim 1, is characterized in that, its number average molecular weight is between 30,000～600,000.
5. coupled copolymer as claimed in claim 1, is characterized in that, the described organoalkoxysilane coupler containing the alkenyl functional group selects free vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl three butoxy silanes, vinyl oxyethyl group bi-methoxy silane, the two propoxy-silane of vinyl oxyethyl group, the two butoxy silanes of vinyl oxyethyl group, the two (ethoxymethyl) TMOSs of vinyl, the two ethoxy-c TMOSs of vinyl, the two oxyethyl group butoxy silanes of vinyl, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, propenyl tripropoxy silane, propenyl three butoxy silanes, propenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of propenyl oxyethyl group, the two butoxy silanes of propenyl oxyethyl group, the two (ethoxymethyl) TMOSs of propenyl, the two ethoxy-c TMOSs of propenyl, the two oxyethyl group butoxy silanes of propenyl, the butenyl Trimethoxy silane, the butenyl triethoxyl silane, butenyl tripropoxy silane, butenyl three butoxy silanes, butenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of butenyl oxyethyl group, the two butoxy silanes of butenyl oxyethyl group, the two (ethoxymethyl) TMOSs of butenyl, the two ethoxy-c TMOSs of butenyl, the two oxyethyl group butoxy silanes of butenyl, the pentenyl Trimethoxy silane, the pentenyl triethoxyl silane, pentenyl tripropoxy silane, pentenyl three butoxy silanes, pentenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of pentenyl oxyethyl group, the two butoxy silanes of pentenyl oxyethyl group, the two (ethoxymethyl) TMOSs of pentenyl, the two ethoxy-c TMOSs of pentenyl, the two oxyethyl group butoxy silanes of pentenyl, the hexenyl Trimethoxy silane, the hexenyl triethoxyl silane, hexenyl tripropoxy silane, hexenyl three butoxy silanes, hexenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of hexenyl oxyethyl group, the two butoxy silanes of hexenyl oxyethyl group, the two (ethoxymethyl) TMOSs of hexenyl, the two ethoxy-c TMOSs of hexenyl, the two oxyethyl group butoxy silanes of hexenyl, two (vinyl-dimethyl oxygen base is silica-based) methane, two (vinyl-dimethyl oxygen base is silica-based) ethane, two (vinyl-dimethyl oxygen base is silica-based) propane, two (vinyl-dimethyl oxygen base is silica-based) butane, two (the vinyl diethoxy is silica-based) methane, two (the vinyl diethoxy is silica-based) ethane, two (the vinyl diethoxy is silica-based) propane, two (the vinyl diethoxy is silica-based) butane, two (the vinyl dipropoxy is silica-based) methane, two (the vinyl dipropoxy is silica-based) ethane, two (the vinyl dipropoxy is silica-based) propane, two (the vinyl dipropoxy is silica-based) butane, two (the vinyl dibutoxy is silica-based) methane, two (the vinyl dibutoxy is silica-based) ethane, two (the vinyl dibutoxy is silica-based) propane, two (the vinyl dibutoxy is silica-based) butane, two (the propenyl dimethoxy is silica-based) methane, two (the propenyl dimethoxy is silica-based) ethane, two (the propenyl dimethoxy is silica-based) propane, two (the propenyl dimethoxy is silica-based) butane, two (the propenyl diethoxy is silica-based) methane, two (the propenyl diethoxy is silica-based) ethane, two (the propenyl diethoxy is silica-based) propane, two (the propenyl diethoxy is silica-based) butane, two (the propenyl dipropoxy is silica-based) methane, two (the propenyl dipropoxy is silica-based) ethane, two (the propenyl dipropoxy is silica-based) propane, two (the propenyl dipropoxy is silica-based) butane, two (the propenyl dibutoxy is silica-based) methane, two (the propenyl dibutoxy is silica-based) ethane, two (the propenyl dibutoxy is silica-based) propane, two (the propenyl dibutoxy is silica-based) butane, two (the butenyl dimethoxy is silica-based) methane, two (the butenyl dimethoxy is silica-based) ethane, two (the butenyl dimethoxy is silica-based) propane, two (the butenyl dimethoxy is silica-based) butane, two (the butenyl diethoxy is silica-based) methane, two (the butenyl diethoxy is silica-based) ethane, two (the butenyl diethoxy is silica-based) propane, two (the butenyl diethoxy is silica-based) butane, two (the butenyl dipropoxy is silica-based) methane, two (the butenyl dipropoxy is silica-based) ethane, two (the butenyl dipropoxy is silica-based) propane, two (the butenyl dipropoxy is silica-based) butane, two (the pentenyl dimethoxy is silica-based) methane, two (the pentenyl dimethoxy is silica-based) ethane, two (the pentenyl dimethoxy is silica-based) propane, two (the pentenyl dimethoxy is silica-based) butane, two (the pentenyl diethoxy is silica-based) methane, two (the pentenyl diethoxy is silica-based) ethane, two (the pentenyl diethoxy is silica-based) propane, two (the pentenyl diethoxy is silica-based) butane, two (the pentenyl dipropoxy is silica-based) methane, two (the pentenyl dipropoxy is silica-based) ethane, two (the pentenyl dipropoxy is silica-based) propane, two (the pentenyl dipropoxy is silica-based) butane, two (the pentenyl dibutoxy is silica-based) methane, two (the pentenyl dibutoxy is silica-based) ethane, two (the pentenyl dibutoxy is silica-based) propane, two (the pentenyl dibutoxy is silica-based) butane, two (the hexenyl dimethoxy is silica-based) methane, two (the hexenyl dimethoxy is silica-based) ethane, two (the hexenyl dimethoxy is silica-based) propane, two (the hexenyl dimethoxy is silica-based) butane, two (the hexenyl diethoxy is silica-based) methane, two (the hexenyl diethoxy is silica-based) ethane, two (the hexenyl diethoxy is silica-based) propane, two (the hexenyl diethoxy is silica-based) butane, two (the hexenyl dipropoxy is silica-based) methane, two (the hexenyl dipropoxy is silica-based) ethane, two (the hexenyl dipropoxy is silica-based) propane, two (the hexenyl dipropoxy is silica-based) butane, two (the hexenyl dibutoxy is silica-based) methane, two (the hexenyl dibutoxy is silica-based) ethane, two (the hexenyl dibutoxy is silica-based) propane, in the group that two (the hexenyl dibutoxy is silica-based) butane and derivative thereof form.
6. a method of manufacturing coupled copolymer, it comprises following steps: (a) utilize organolithium compound to carry out polymerization to conjugated diolefine and vinyl aromatic hydrocarbon monomer, obtain having the multipolymer of lithium terminal group; (b) add this multipolymer with lithium terminal group to carry out coupled reaction the one organoalkoxysilane coupler containing the alkenyl functional group, form thus a coupled copolymer, wherein this mol ratio with consumption of the multipolymer of lithium terminal group and this coupler is 1.4～6.67, and four arm multipolymer content of formed coupled copolymer are between 10 % by weight～30 % by weight; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure FDA00002281528400031
Formula (I)
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
7. method as claimed in claim 6, is characterized in that, the coupling efficiency of described coupled copolymer is between 60 % by weight～95 % by weight.
8. a hydrogenation coupled copolymer, it is at first to utilize organolithium compound to carry out to conjugated diolefine and vinyl aromatic hydrocarbon monomer the multipolymer that polymerization obtains having the lithium terminal group, then this is had the lithium terminal group multipolymer and one containing the organoalkoxysilane coupler of alkenyl functional group in molar ratio 1.4～6.67 use quantitative response, via hydrogenation, obtain again, it is characterized in that, four arm multipolymer content of described hydrogenation coupled copolymer are between 10 % by weight～30 % by weight; Wherein should be containing organoalkoxysilane coupler of alkenyl functional group just like the chemical formula shown in formula (I):
Figure FDA00002281528400041
Formula (I)
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
9. hydrogenation coupled copolymer as claimed in claim 8, it is characterized in that, described vinylaromatic hydrocarbon is selected from vinylbenzene, alpha-methyl styrene, contraposition ethyl styrene, phenylcyclohexane ethene, contraposition vinyl toluene, ortho position vinyl toluene, a position vinyl toluene, 1-vinyl-5-hexyl naphthalene and vinylnaphthalene.
10. hydrogenation coupled copolymer as claimed in claim 8, is characterized in that, described conjugated diolefine is selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, isoprene, m-pentadiene and 2-phenyl-1,3-butadiene.
11. hydrogenation coupled copolymer as claimed in claim 8, is characterized in that, its number average molecular weight is between 30,000～600,000.
12. hydrogenation coupled copolymer as claimed in claim 8, is characterized in that, the described organoalkoxysilane coupler containing the alkenyl functional group selects free vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl three butoxy silanes, vinyl oxyethyl group bi-methoxy silane, the two propoxy-silane of vinyl oxyethyl group, the two butoxy silanes of vinyl oxyethyl group, the two (ethoxymethyl) TMOSs of vinyl, the two ethoxy-c TMOSs of vinyl, the two oxyethyl group butoxy silanes of vinyl, the propenyl Trimethoxy silane, the propenyl triethoxyl silane, propenyl tripropoxy silane, propenyl three butoxy silanes, propenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of propenyl oxyethyl group, the two butoxy silanes of propenyl oxyethyl group, the two (ethoxymethyl) TMOSs of propenyl, the two ethoxy-c TMOSs of propenyl, the two oxyethyl group butoxy silanes of propenyl, the butenyl Trimethoxy silane, the butenyl triethoxyl silane, butenyl tripropoxy silane, butenyl three butoxy silanes, butenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of butenyl oxyethyl group, the two butoxy silanes of butenyl oxyethyl group, the two (ethoxymethyl) TMOSs of butenyl, the two ethoxy-c TMOSs of butenyl, the two oxyethyl group butoxy silanes of butenyl, the pentenyl Trimethoxy silane, the pentenyl triethoxyl silane, pentenyl tripropoxy silane, pentenyl three butoxy silanes, pentenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of pentenyl oxyethyl group, the two butoxy silanes of pentenyl oxyethyl group, the two (ethoxymethyl) TMOSs of pentenyl, the two ethoxy-c TMOSs of pentenyl, the two oxyethyl group butoxy silanes of pentenyl, the hexenyl Trimethoxy silane, the hexenyl triethoxyl silane, hexenyl tripropoxy silane, hexenyl three butoxy silanes, hexenyl oxyethyl group bi-methoxy silane, the two propoxy-silane of hexenyl oxyethyl group, the two butoxy silanes of hexenyl oxyethyl group, the two (ethoxymethyl) TMOSs of hexenyl, the two ethoxy-c TMOSs of hexenyl, the two oxyethyl group butoxy silanes of hexenyl, two (vinyl-dimethyl oxygen base is silica-based) methane, two (vinyl-dimethyl oxygen base is silica-based) ethane, two (vinyl-dimethyl oxygen base is silica-based) propane, two (vinyl-dimethyl oxygen base is silica-based) butane, two (the vinyl diethoxy is silica-based) methane, two (the vinyl diethoxy is silica-based) ethane, two (the vinyl diethoxy is silica-based) propane, two (the vinyl diethoxy is silica-based) butane, two (the vinyl dipropoxy is silica-based) methane, two (the vinyl dipropoxy is silica-based) ethane, two (the vinyl dipropoxy is silica-based) propane, two (the vinyl dipropoxy is silica-based) butane, two (the vinyl dibutoxy is silica-based) methane, two (the vinyl dibutoxy is silica-based) ethane, two (the vinyl dibutoxy is silica-based) propane, two (the vinyl dibutoxy is silica-based) butane, two (the propenyl dimethoxy is silica-based) methane, two (the propenyl dimethoxy is silica-based) ethane, two (the propenyl dimethoxy is silica-based) propane, two (the propenyl dimethoxy is silica-based) butane, two (the propenyl diethoxy is silica-based) methane, two (the propenyl diethoxy is silica-based) ethane, two (the propenyl diethoxy is silica-based) propane, two (the propenyl diethoxy is silica-based) butane, two (the propenyl dipropoxy is silica-based) methane, two (the propenyl dipropoxy is silica-based) ethane, two (the propenyl dipropoxy is silica-based) propane, two (the propenyl dipropoxy is silica-based) butane, two (the propenyl dibutoxy is silica-based) methane, two (the propenyl dibutoxy is silica-based) ethane, two (the propenyl dibutoxy is silica-based) propane, two (the propenyl dibutoxy is silica-based) butane, two (the butenyl dimethoxy is silica-based) methane, two (the butenyl dimethoxy is silica-based) ethane, two (the butenyl dimethoxy is silica-based) propane, two (the butenyl dimethoxy is silica-based) butane, two (the butenyl diethoxy is silica-based) methane, two (the butenyl diethoxy is silica-based) ethane, two (the butenyl diethoxy is silica-based) propane, two (the butenyl diethoxy is silica-based) butane, two (the butenyl dipropoxy is silica-based) methane, two (the butenyl dipropoxy is silica-based) ethane, two (the butenyl dipropoxy is silica-based) propane, two (the butenyl dipropoxy is silica-based) butane, two (the butenyl dibutoxy is silica-based) methane, two (the butenyl dibutoxy is silica-based) ethane, two (the butenyl dibutoxy is silica-based) propane, two (the butenyl dibutoxy is silica-based) butane, two (the pentenyl dimethoxy is silica-based) methane, two (the pentenyl dimethoxy is silica-based) ethane, two (the pentenyl dimethoxy is silica-based) propane, two (the pentenyl dimethoxy is silica-based) butane, two (the pentenyl diethoxy is silica-based) methane, two (the pentenyl diethoxy is silica-based) ethane, two (the pentenyl diethoxy is silica-based) propane, two (the pentenyl diethoxy is silica-based) butane, two (the pentenyl dipropoxy is silica-based) methane, two (the pentenyl dipropoxy is silica-based) ethane, two (the pentenyl dipropoxy is silica-based) propane, two (the pentenyl dipropoxy is silica-based) butane, two (the pentenyl dibutoxy is silica-based) methane, two (the pentenyl dibutoxy is silica-based) ethane, two (the pentenyl dibutoxy is silica-based) propane, two (the pentenyl dibutoxy is silica-based) butane, two (the hexenyl dimethoxy is silica-based) methane, two (the hexenyl dimethoxy is silica-based) ethane, two (the hexenyl dimethoxy is silica-based) propane, two (the hexenyl dimethoxy is silica-based) butane, two (the hexenyl diethoxy is silica-based) methane, two (the hexenyl diethoxy is silica-based) ethane, two (the hexenyl diethoxy is silica-based) propane, two (the hexenyl diethoxy is silica-based) butane, two (the hexenyl dipropoxy is silica-based) methane, two (the hexenyl dipropoxy is silica-based) ethane, two (the hexenyl dipropoxy is silica-based) propane, two (the hexenyl dipropoxy is silica-based) butane, two (the hexenyl dibutoxy is silica-based) methane, two (the hexenyl dibutoxy is silica-based) ethane, two (the hexenyl dibutoxy is silica-based) propane, in the group that two (the hexenyl dibutoxy is silica-based) butane and derivative thereof form.
13. hydrogenation coupled copolymer as claimed in claim 8, is characterized in that, the hydrogenation ratio of described conjugated diene unit is higher than 50%, and vinylaromatic hydrocarbon unit hydrogenation ratio is lower than 10%.
14. hydrogenation coupled copolymer as claimed in claim 8, is characterized in that, the ratio of the ratio of its hydrogenation post polymerization thing coupling rate/hydrogenation prepolymer coupling rate and hydrogenation post polymerization thing four arm product content/hydrogenation prepolymer four arm product content is greater than 0.7.
15. a method of manufacturing the hydrogenation coupled copolymer, it comprises following steps: (a) utilize organolithium compound to carry out polymerization to conjugated diolefine and vinyl aromatic hydrocarbon monomer, obtain having the multipolymer of lithium terminal group; (b) add this multipolymer with lithium terminal group to carry out coupled reaction the one organoalkoxysilane coupler containing the alkenyl functional group, form thus a coupled copolymer, wherein this mol ratio with consumption of the multipolymer of lithium terminal group and this coupler is 1.4～6.67; (c) this coupled copolymer of hydrogenation, form a hydrogenation coupled copolymer thus, and four arm multipolymer content of formed hydrogenation coupled copolymer are between 10 % by weight～30 % by weight; Wherein should contain the chemical formula of the organoalkoxysilane coupler of alkenyl functional group just like formula (I):
Figure FDA00002281528400061
Formula (I)
R wherein 1with R 4for identical or different C 1-6alkyl, R 3for C 2-6containing the alkenyl functional group, R 5for C 1-6alkyl or alkoxyl group or C 2-6thiazolinyl, q is 1 or 0; When q=0, k=j=0, and R 2for C 1-6alkoxyl group, 1≤n≤3,0≤m≤2, m+n=3; When q=1, k+j=3, and R 2for-(CH 2) r-, r=1～6, m+n=3.
16. method as claimed in claim 15, is characterized in that, the coupling efficiency of described hydrogenation coupled copolymer is between 60 % by weight～95 % by weight.
CN 201010156457 2010-04-01 2010-04-01 Coupled copolymer and preparation method thereof Active CN102212196B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010156457 CN102212196B (en) 2010-04-01 2010-04-01 Coupled copolymer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010156457 CN102212196B (en) 2010-04-01 2010-04-01 Coupled copolymer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102212196A CN102212196A (en) 2011-10-12
CN102212196B true CN102212196B (en) 2013-03-06

Family

ID=44743751

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010156457 Active CN102212196B (en) 2010-04-01 2010-04-01 Coupled copolymer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102212196B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661298A2 (en) * 1993-12-29 1995-07-05 Bridgestone Corporation Diene polymers and copolymers having an alkoxysilane group
CN1105037A (en) * 1993-11-09 1995-07-12 国际壳牌研究有限公司 Dissimilar arm asymmetric radial or star block copolymers for adhesives and sealants

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105037A (en) * 1993-11-09 1995-07-12 国际壳牌研究有限公司 Dissimilar arm asymmetric radial or star block copolymers for adhesives and sealants
EP0661298A2 (en) * 1993-12-29 1995-07-05 Bridgestone Corporation Diene polymers and copolymers having an alkoxysilane group

Also Published As

Publication number Publication date
CN102212196A (en) 2011-10-12

Similar Documents

Publication Publication Date Title
CA2042438C (en) Selective hydrogenation of conjugated diolefin polymers
TWI405781B (en) Coupled polymers and manufacturing methods thereof
CA3022162C (en) Polar modifier systems for high vinyl block copolymerization
JPH07116272B2 (en) Vulcanizable liquid composition
JP2005509066A (en) Linear block copolymer and method for producing the same
EP0745614B1 (en) Synthesis of siloxane-functional telechelic hydrocarbon polymers
KR20160075127A (en) Novel initiator in anionic polymerization and method for preparing a conjugated diene polymer using the same
JPH08512067A (en) Solid elastomer block copolymer
US3855189A (en) Polar compounds improve effectiveness of polyvinyl aromatic compounds
EP0745613A1 (en) Synthesis of silyl-functional telechelic hydrocarbon polymers
CN1911969B (en) Process for the selective hydrogenation of unsaturated (co)polymers
US7700694B2 (en) Catalyst composition and method for hydrogenating a polymer having a conjugated diene
US3801554A (en) Lithium alkenoxides as modifiers in organolithium initiated polymerization
CN107337754B (en) Conjugated diene polymer, preparation method thereof, polybutadiene and polyisoprene
US20230094374A1 (en) Polar Modifier Systems for High Vinyl Block Copolymerization
KR20010043677A (en) Process for making anionic polymeric di- and polyfunctional polymers using protected functional initiators
CN102212196B (en) Coupled copolymer and preparation method thereof
JP2712622B2 (en) Method for producing conjugated diene polymer
CN1134714A (en) Hydrogenated asymmetric radial copolymers
CN100537626C (en) Process for making a coupled low vinyl block copolymer composition and the resulting composition
CN1137174C (en) Application of polychela-type trigger in preparing biblock rubber of conjugated diolefine and monovinyl arene
CN115260395B (en) Crystalline thermoplastic elastomer and preparation method thereof
CN1317506A (en) Conjugated biolofin and monovinylarene dual-block rubber with high wet skid resistance and low rolling resistance
JP2003301113A (en) Asphalt composition
JPS58136604A (en) Production of polydiene/polypeptide block copolymer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant