CN102321214B - Polyethylene containing silicon-hydrogen reactive group on side group and preparation method thereof - Google Patents
Polyethylene containing silicon-hydrogen reactive group on side group and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer material synthesis and preparation, relating to a polymer which is a random copolymer consisting of polyethylene and silicon-hydrogen reactive group containing poly (4-vinyl phenyl dimethyl silane) and a preparation method thereof. The polymer is characterized in that: measuring according to the polymer mass of 100 percent, mass percentage of the polyethylene content is 80-99.5 percent, and mass percentage of the poly (4-vinyl phenyl dimethyl silane) content is 0.5-20 percent; the number average molecular weight of the polymer is 5*10<3>-100*10<4>; and the polyethylene containing a silicon-hydrogen reactive group on a side group is prepared from polybutadiene and a poly (4-vinyl phenyl dimethyl silane) copolymer through a hydrogenation reaction. The effect and benefit of the invention is to provide a functionalized polyethylene containing the silicon-hydrogen reactive group on the side group, and the functionalized polyethylene has wide application prospects in the field of functionalized polyethylene materials.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a class side group and contain silicon H-H reaction group polyethylene, the random copolymers being formed by polyethylene and poly-(the 4-ethenylphenyl dimethylsilane) that contain silicon H-H reaction group.
Background technology
Though polyethylene excellent property and being widely used, it is mainly comprised of carbon, two kinds of atoms of hydrogen, belongs to non-polar polymer, thereby has limited its application in fields such as bonding, printing, photoelectron material, biomaterials.In poly functional modification, side group functional poly ethene is a very important class, and the polyethylene that side group contains reactive group is a kind of new poly effective ways of synthetic side group functionalization.This method is that the common monomer with reactive group is incorporated in polyethylene through copolymerization, then utilize the chemical property that reactive group is active, optionally on this reactive group, carry out various Functional Conversion reactions, and then obtain various side group functional poly ethene.The polyethylene of this side group functionalization can improve polythene material in the application in the fields such as bonding, printing, photoelectron material, biomaterial, has wide practical use.
The two key groups of the boron alkyl that character is active and vinylbenzene etc. all belong to reactive group, reactive group can be converted into various functional groups, as hydroxyl, carboxyl, amino etc. by chemical reaction.And silicon hydrogen group can be well carries out addition reaction of silicon with hydrogen with the compound that contains functional groups and end and have two keys, also can introduce several functions group.If can synthesize the polyethylene that side group contains si-h bond, then by addition reaction of silicon with hydrogen, introduce several functions group and obtain various side group functional poly ethene.
Document (polymer circular, 2009, (1): 1-15) disclose polyolefinic methods such as commenting synthetic side group functional poly ethene, polypropylene, adopt Ziegler-Natta and metallocene catalyst can be contained by the synthetic side group of coordination polymerization process the polyolefine of boron alkyl and the two keys of vinylbenzene, utilize the two key groups of the active boron alkyl of character and vinylbenzene, introduce various functional groups, as hydroxyl, carboxyl, amino etc., synthesize side group functional polyolefin.The polyolefine such as the polyethylene that does not occur containing si-h bond reactive group in its disclosed method, polypropylene.
Divinyl, by adopting living anion polymerization technology, can synthesize the polyhutadiene with definite molecular weight and molecular weight distribution, microtexture and Composition distribution of copolymer.Because the hydrogenation reaction of unsaturated double-bond in polyhutadiene can not affect the molecular weight of polymkeric substance and molecular weight distribution, chain structure equimolecular parameter, the hydrogenation of polyhutadiene that so just can be by corresponding molecular chain structure is prepared the polyethylene of different molecular structures parameter.Since can prepare polyethylene by the hydrogenation of polyhutadiene, when divinyl carries out living anion polymerization, add so a kind of copolymerizable monomer with reactive group, finally this copolymer hydrogenating just can be obtained to the polyethylene that side group contains reactive group.
4-ethenylphenyl dimethylsilane monomer has silicon hydrogen group, can be incorporated in polyhutadiene through anionic polymerization, and silicon hydrogen group can carry out addition reaction of silicon with hydrogen with the compound that contains functional groups and end and have two keys, and then synthetic side group functional poly ethene.Document (Journal Polymer Science, Part A, 1996,34 (8): 1543-1552) disclose a kind of polyethylene that contains silicon hydrogen group at macromolecular chain end that synthesizes, by initiated polymerization divinyl and with dimethylchlorosilane, reactive polymer is carried out to end-blocking, synthesized the polyhutadiene that end contains silicon hydrogen group, then opposite end base band has the polyhutadiene of silicon hydrogen group to carry out the last polyethylene that contains silicon hydrogen group at the end of the chain that obtains of hydrogenation reaction.In its disclosed method, there is not polyhutadiene and the polyethylene that side group contains si-h bond reactive group.
Summary of the invention
The invention provides a class side group and contain silicon H-H reaction group polyethylene, polymkeric substance is the random copolymers that polyethylene and poly-(the 4-ethenylphenyl dimethylsilane) that contains silicon H-H reaction group form, and by polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, through hydrogenation reaction, is prepared.Wherein polyethylene partly has crystallinity, and gather (4-ethenylphenyl dimethylsilane) part, there is silicon H-H reaction group, this silicon hydrogen group can with contain functional groups (as groups such as epoxide group, fluorine atom, liquid crystal units) and the end compound with carbon-carbon double bond and carry out addition reaction of silicon with hydrogen, thereby prepare functional poly vinyl material.Can improve polythene material in the application in the fields such as bonding, printing, photoelectron material, biomaterial, have wide practical use.
Side group involved in the present invention contains the random copolymers that silicon H-H reaction group polyethylene is comprised of polyethylene and poly-(the 4-ethenylphenyl dimethylsilane) that contain silicon H-H reaction group; In total polymer mass 100%, polymerized ethylene content mass percent general range is 80%-99.5%, and optimum range is 90%-99%; Poly-(4-ethenylphenyl dimethylsilane) content mass percent general range is 0.5%-20%, and optimum range is 1%-10%; The number-average molecular weight general range of polymkeric substance is 5 * 10
3-100 * 10
4, optimum range is 1 * 10
4-80 * 10
4.
The side group the present invention relates to contains the single type chain structure that the poly polymer molecular chain of silicon H-H reaction group is comprised of linear structure, three arm branched structures, four arms asteroids and the hybrid architecture being comprised of three kinds of structures thereof.
For synthetic side group contains silicon H-H reaction group polyethylene, the present invention carries out hydrogenation reaction by remaining carbon-carbon double bond in polyhutadiene part in polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer.
The random copolymers that polyhutadiene involved in the present invention and poly-(4-ethenylphenyl dimethylsilane) multipolymer are comprised of polyhutadiene and poly-(the 4-ethenylphenyl dimethylsilane) that contain silicon H-H reaction group.
In polyhutadiene involved in the present invention and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in total polymer mass 100%, polybutadiene content mass percent general range is 80%-99%, and optimum range is 90%-98%; Poly-(4-ethenylphenyl dimethylsilane) content mass percent general range is 1%-20%, and optimum range is 10%-12%; The number-average molecular weight general range of polymkeric substance is 4 * 10
3-100 * 10
4, optimum range is 1 * 10
4-80 * 10
4.
In polyhutadiene involved in the present invention and poly-(4-ethenylphenyl dimethylsilane) multipolymer in polyhutadiene total mass 100%, in polyhutadiene 1,4-structural content mass percent general range is 60%-94%, and optimum range is 80%-90%; 1,2-structural content mass percent general range is 6%-40%, and optimum range is 10%-20%.
The polyethylene that contains silicon H-H reaction group in order to synthesize side group, the present invention adds hydrogenation by remaining carbon-carbon double bond in polyhutadiene part in polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, and the degree of hydrogenation of carbon-carbon double bond is 95%-100%.
Effect of the present invention and benefit have been to provide the functional poly ethene that a kind of side group contains silicon H-H reaction group, in Functional Polyolefins field, have wide practical use.
Embodiment
The present invention proposes following examples as further instruction, but and the scope of unrestricted the claims in the present invention protection.
Embodiment 1
In 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 49 grams of divinyl, 1 gram of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium, start to carry out anionic copolymerization and close, butyllithium consumption is 1 * 10 by the number-average molecular weight of polymkeric substance
4metering, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer.In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2: 2: 1.After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms.
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 93%, 1,2-structural content mass percent is 7% (mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 98.2%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 1.8%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 1.1 * 10
4, molecular weight distributing index is 1.20; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 106.1 ℃, and degree of crystallinity is 40.2%.
Embodiment 2
In 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 48 grams of divinyl, 2 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium, start to carry out anionic copolymerization and close, butyllithium consumption is 3 * 10 by the number-average molecular weight of polymkeric substance
4metering, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer.In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2: 2: 1.After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms.
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 92%, 1,2-structural content mass percent is 8% (mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 96.3%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 3.7%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 3.4 * 10
4, molecular weight distributing index is 1.25; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 105.4 ℃, and degree of crystallinity is 26.2%.
Embodiment 3
In 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 45 grams of divinyl, 5 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium and tetrahydrofuran (THF), start to carry out anionic copolymerization and close, butyllithium consumption is 8 * 10 by the number-average molecular weight of polymkeric substance
4metering, the consumption of tetrahydrofuran (THF) is to be 0.5: 1 with n-Butyl Lithium mol ratio, and polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer.In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2: 2: 1.After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms.
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 84%, 1,2-structural content mass percent is 16% (mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 90.2%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 9.8%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 9.1 * 10
4, molecular weight distributing index is 1.30; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 80.1 ℃, and degree of crystallinity is 17.2%.
Embodiment 4
In 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 43 grams of divinyl, 7 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium and tetrahydrofuran (THF), start to carry out anionic copolymerization and close, butyllithium consumption is 20 * 10 by the number-average molecular weight of polymkeric substance
4metering, the consumption of tetrahydrofuran (THF) is to be 2.5: 1 with n-Butyl Lithium mol ratio, and polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer.In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2: 2: 1.After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms.
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 78%, 1,2-structural content mass percent is 22% (mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 86.4%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 13.6%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 19.6 * 10
4, molecular weight distributing index is 1.32; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 40.1 ℃, and degree of crystallinity is 6.2%.
Claims (4)
1. a class side group contains the poly preparation method of silicon H-H reaction group, it is characterized in that: in 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 49 grams of divinyl, 1 gram of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium, start to carry out anionic copolymerization and close, butyllithium consumption is 1 * 10 by the number-average molecular weight of polymkeric substance
4metering, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer; In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2:2:1; After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms;
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 93%, 1,2-structural content mass percent is 7%(mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 98.2%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 1.8%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 1.1 * 10
4, molecular weight distributing index is 1.20; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 106.1 ℃, and degree of crystallinity is 40.2%.
2. a class side group contains the poly preparation method of silicon H-H reaction group, it is characterized in that: in 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 48 grams of divinyl, 2 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium, start to carry out anionic copolymerization and close, butyllithium consumption is 3 * 10 by the number-average molecular weight of polymkeric substance
4metering, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer; In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2:2:1; After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms;
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 92%, 1,2-structural content mass percent is 8%(mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 96.3%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 3.7%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 3.4 * 10
4, molecular weight distributing index is 1.25; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 105.4 ℃, and degree of crystallinity is 26.2%;
3. a class side group contains the poly preparation method of silicon H-H reaction group, it is characterized in that: in 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 45 grams of divinyl, 5 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium and tetrahydrofuran (THF), start to carry out anionic copolymerization and close, butyllithium consumption is 8 * 10 by the number-average molecular weight of polymkeric substance
4metering, the consumption of tetrahydrofuran (THF) is to be 0.5:1 with n-Butyl Lithium mol ratio, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer; In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2:2:1; After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms;
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 84%, 1,2-structural content mass percent is 16%(mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 90.2%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 9.8%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 9.1 * 10
4, molecular weight distributing index is 1.30; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 80.1 ℃, and degree of crystallinity is 17.2%.
4. a class side group contains the poly preparation method of silicon H-H reaction group, it is characterized in that: in 1 liter of stainless steel cauldron with stirring, add 0.65 liter of hexanaphthene, 43 grams of divinyl, 7 grams of 4-ethenylphenyl dimethylsilane, be warmed up to 50 ℃, with syringe, inject the cyclohexane solution of n-Butyl Lithium and tetrahydrofuran (THF), start to carry out anionic copolymerization and close, butyllithium consumption is 20 * 10 by the number-average molecular weight of polymkeric substance
4metering, the consumption of tetrahydrofuran (THF) is to be 2.5:1 with n-Butyl Lithium mol ratio, polyreaction finishes rear cool to room temperature, product dehydrated alcohol sedimentation, vacuum-drying 24h, to constant weight, obtains polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer; In 250 milliliters of there-necked flasks, 1.2g multipolymer is dissolved in 60 milliliters of o-Xylols, after fully dissolving, add successively p-toluene sulfonyl hydrazide 8.3g, 8.5 milliliters of tripropyl amines, in p-toluene sulfonyl hydrazide, tripropyl amine and polymkeric substance, in polyhutadiene, the mol ratio of carbon-carbon double bond is 2:2:1; After refluxing 4 hours, stop heating at 135～140 ℃, after being cooled to room temperature, system is settled out product washing several with ethanol, then with dilute hydrochloric acid, wash, finally with hot deionized water, wash, product is dried 24 hours at 60 ℃ in vacuum drying oven, the random copolymers that poly-(the 4-ethenylphenyl dimethylsilane) that finally obtains polyethylene and contain silicon H-H reaction group forms;
Adopt the microstructure analysis test of infrared spectrometer to polyhutadiene and poly-(4-ethenylphenyl dimethylsilane) multipolymer, in multipolymer 1 of polyhutadiene part, 4-structural content mass percent is 78%, 1,2-structural content mass percent is 22%(mass percent, in monomer divinyl total amount 100%); Employing nuclear magnetic resonance spectroscopy(NMR spectroscopy) (
1h-NMR) polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers are carried out to analytical test, in multipolymer, polyethylene part content mass percent is 86.4%, poly-(4-ethenylphenyl dimethylsilane) part content mass percent is 13.6%, and in polyhutadiene part, the hydrogenation degree of remaining carbon-carbon double bond is 99%; Adopt gel permeation chromatograph to carry out analytical test to molecular weight and the distribution of polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the number-average molecular weight of segmented copolymer is 19.6 * 10
4, molecular weight distributing index is 1.32; Adopt poor formula scanning calorimetry to carry out analytical test to polyethylene and poly-(4-ethenylphenyl dimethylsilane) random copolymers, the crystalline melt temperature of multipolymer is 40.1 ℃, and degree of crystallinity is 6.2%.
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