CN106243258A - A kind of vistanex and preparation method and application - Google Patents

A kind of vistanex and preparation method and application Download PDF

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Publication number
CN106243258A
CN106243258A CN201610631922.1A CN201610631922A CN106243258A CN 106243258 A CN106243258 A CN 106243258A CN 201610631922 A CN201610631922 A CN 201610631922A CN 106243258 A CN106243258 A CN 106243258A
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Prior art keywords
vistanex
polymer
lithium
solvent
preparation
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CN201610631922.1A
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Chinese (zh)
Inventor
倪国兰
王卫东
马相亭
候福顺
孙育成
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Suzhou Shuanghu Chemical Technology Co Ltd
CITIC National Chemical Co Ltd
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Suzhou Shuanghu Chemical Technology Co Ltd
CITIC National Chemical Co Ltd
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Priority to CN201610631922.1A priority Critical patent/CN106243258A/en
Publication of CN106243258A publication Critical patent/CN106243258A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06Butadiene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08Isoprene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/463Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from sodium or potassium
    • C08F4/465Metalic sodium or potassium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/46Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
    • C08F4/48Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium
    • C08F4/482Metallic lithium, rubidium, caesium or francium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/04Reduction, e.g. hydrogenation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a kind of vistanex and preparation method and application.Described vistanex, there is monomeric unit and the monomeric unit derived from least one alhpa olefin selected from propylene, butylene or methyl 1 amylene of derived from ethylene, described vistanex is polymer, and polydispersity coefficient PDI is less than 1.5, and the content of ashes of polymer is less than 10ppm.The monodispersity of the vistanex of the present invention is good, can give full play to the performance of vistanex.The content of ashes of resin is low, and the transparency of product is good, and ageing-resistant ability is strong.It is suitable for manufacturing the product having particular/special requirement to product transparency, insulating properties and life-span etc., such as battery membranes etc..It also is suitable as additive to add in other polyolefine material and enhance product performance.

Description

A kind of vistanex and preparation method and application
Technical field
The present invention relates to a kind of vistanex.Specifically, the present invention relates to that there is monodispersity and content of ashes is non- The lowest vistanex, its preparation method and application thereof.
Background technology
Polyolefin major part is to be produced by traditional Ziegler-Natta catalyst, and Ziegler-Natta catalyst is A kind of polydisperse catalyst system, has the catalyst center of various active in system, its polyolefin produced also has many points Dissipating feature, molecular weight distribution (PDI, polydispersity coefficient, for characterizing the molecular weight distribution of polymer) is more than 5.Due to The polydispersion characteristic of Ziegler-Natta catalyst system and catalyzing, it is poor to polyolefinic molecular weight and molecular structure control ability, product Performance is worse than monodispersed polyolefin products.
Metallocene catalyst can produce the polyolefin (PDI is 2 ~ 3) with preferable single dispersing character, but relative to strictly Monodisperse system (PDI < 1.5) in meaning, the molecular weight distribution of metallocene-polyolefin product is the widest.
Polyolefinic performance is had an impact by the content of ashes in polyolefin.Ash in polyolefin typically catalyst and helping The residual of catalyst, it not only can affect the transparency of polyolefin products, crystallinity, and the metal component in ash also can accelerate to gather The oxidation of alkene and degraded, affect properties of product and life-span.
Therefore, current present situation is, is still required for a kind of vistanex, its monodispersity having had and low ash Content, it is possible to more preferably embody the performance of polyolefin itself.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of vistanex and preparation method thereof with Application.
A kind of vistanex, have the monomeric unit of derived from ethylene with derived from selected from propylene, butylene or methyl isophthalic acid- The monomeric unit of at least one alpha-olefin of amylene, described vistanex is polymer, and polydispersity coefficient PDI is less than 1.5, The content of ashes of polymer is less than 10ppm.
Described density polymer is 0.88 ~ 0.98g/cm3, polymer molecular weight is adjustable in the range of 1000 ~ 200000, institute The content of the monomeric unit stating derived from propylene, butylene and Methyl-1-pentene is 0.2 ~ 20 weight %.
A kind of preparation method of the vistanex described in basis, step includes:
In atent solvent, the anion of 1,3-butadiene or isoprene is caused with the organic compound of lithium metal or metallic sodium Polymerization prepares polymer glue;
Metal in removing polymer glue;
Spent hydroprocessing catalyst carries out catalytic hydrogenation and produces olefin polymer polymer glue;With
Described olefin polymer is obtained after separating hydrogenation catalyst and solvent.
The organic compound of described lithium metal or metallic sodium is selected from lithium or the alkyl or aryl compound of sodium, preferably is selected from positive fourth Base lithium, isobutyl group lithium, tert-butyl lithium, phenyl lithium and benzyl lithium, more preferably from n-BuLi, isobutyl group lithium and tert-butyl lithium.
Described atent solvent refers to lithium metal or the organic compound of metallic sodium and 1,3-butadiene or isoprene There is no chemically active solvent, preferably be selected from pentane, hexane, hexamethylene, heptane and oxolane or two of which or two or more The combination of solvent, more preferably from hexane, hexamethylene and oxolane or the combination of two of which solvent.
Described hydrogenation catalyst is selected from supported metallic nickel or the catalyst of palladium.
A kind of moulded products, is manufactured according to described vistanex molding by melt-processed.
Beneficial effects of the present invention:
The monodispersity of the vistanex of the present invention is good, can give full play to the performance of vistanex.The content of ashes of resin Low, the transparency of product is good, and ageing-resistant ability is strong.Be suitable for manufacturing has special wanting to product transparency, insulating properties and life-span etc. The product asked, such as battery membranes etc..It also is suitable as additive to add in other polyolefine material and enhance product performance.
The preparation method technique simple possible of the vistanex of the present invention, is suitable for commercial production.
Detailed description of the invention
Below the detailed description of the invention of the present invention is described in detail, it should be noted however that the protection of the present invention Scope is the most limited to these specific embodiments.
The present invention relates to a kind of vistanex, there is the monomeric unit of derived from ethylene and derived from selected from propylene, fourth The monomeric unit of at least one alpha-olefin of alkene or Methyl-1-pentene.
According to the present invention, the microscopic structural units of described vistanex is with ethylene unit as backbone structure, its side chain Structure includes one or more in methyl, ethyl and isopropyl.
According to the present invention, described vistanex has narrow molecular weight distribution, and its molecular weight distribution index is (the most Coefficient of dispersion PDI, with representing that the ratio of Mw/Mn calculates) less than 1.5.
According to the present invention, described vistanex has low content of ashes, and its content of ashes is less than 10ppm.
According to the present invention, the density of described vistanex is 0.88 ~ 0.98g/cm3, polymer molecular weight 1000 ~ In the range of 200000 adjustable, in resin, the content of the monomeric unit of propylene, butylene and Methyl-1-pentene is 0.2 ~ 20 weight %.
According to the present invention, described vistanex is by de-after anionic polymerisation by 1,3-butadiene or isoprene Then metal is hydrogenated with manufacture.
Specifically, the present invention relates to the preparation method of a kind of vistanex, through the following steps that realize:
In atent solvent, the anion of 1,3-butadiene or isoprene is caused with the organic compound of lithium metal and metallic sodium Polymerization prepares the step of polymer glue;
The step of the metal in removing polymer glue;
Spent hydroprocessing catalyst carries out catalytic hydrogenation and produces the step of olefin polymer polymer glue;With
Step by hydrogenated products with olefin polymer described in catalysts and solvents isolated.
According to the present invention, manufacture the raw material of the described vistanex one in 1,3-butadiene and isoprene or The combination of two kinds, the portfolio ratio of two kinds of monomers arbitrarily can regulate from 0:100 to 100:0 according to product needed.
Carry out according to being aggregated in atent solvent of the present invention, starting monomer 1,3-butadiene and isoprene.Described lazy Property solvent refer to polymerization initiator and polymerization monomer 1,3-butadiene and isoprene there is no chemically active solvent, preferably be selected from Pentane, hexane, hexamethylene, heptane and oxolane or two of which or the combination of two or more solvent, more preferably from hexane, ring Hexane and oxolane or the combination of two of which solvent.
According to the present invention, the initiator causing starting monomer 1,3-butadiene and isoprene to carry out being polymerized is a kind of metal Lithium and the organic compound of metallic sodium, this metallo-organic compound has Anionic Polymerization Living, selected from lithium and the alkyl of sodium or virtue Based compound, preferably is selected from n-BuLi, isobutyl group lithium, tert-butyl lithium, phenyl lithium and benzyl lithium, more preferably from n-BuLi, different Butyl lithium and tert-butyl lithium.
According to the present invention, starting monomer 1,3-butadiene and the isoprene concentration in atent solvent is removed heat by reactor Ability and the restriction of polymerization temperature, be generally selected from 5 ~ 30 weight %, preferably is selected from 10 ~ 20 weight %.
It is known that the molecular weight of anionic polymer is controlled by the ratio of starting monomer with initiator.Therefore the present invention The organic compound of middle initiator lithium and sodium and the mol ratio of starting monomer are selected from 20:1 ~ 4000:1.
According to the present invention, the polymerization temperature of starting monomer is selected from 40 ~ 100 DEG C, preferably is selected from 50 ~ 70 DEG C.Polymerization time is selected from 0.2 ~ 4h, preferably is selected from 0.5 ~ 2h.
According to the present invention, after starting monomer has been polymerized, need polymer glue is carried out demetalization process.Many institute's weeks Know, after anionic polymerisation terminates, the metal in initiator presented in polymer metal salt, during demetalization firstly the need of Polymer metal salt is converted into the hydroxide of polymer and metal ion by hydrolysis.The present invention uses and adds in polymer glue The method entering suitable quantity of water carries out demetalization, and water is 2 ~ 10 weight % with the ratio of polymer glue, and preferably 3 ~ 5 weight %, by stirring The mode of mixing makes glue be sufficiently mixed with water and hydrolyze, and hydrolysis time is selected from 0.1 ~ 0.5h, stands and make polymer latex after hydrolysis Liquid is layered with aqueous phase, the method by applying electrostatic field can be selected to accelerate organic facies and separate with aqueous phase.Isolated organic It is the polymer glue after removing metal mutually, can select to obtain demetallated polymer by the method detaching organic facies Glue.
According to the present invention, the hydrogenation reaction of polymer glue is to proceed under hydrogenation catalyst effect.Hydrogenation catalyst Metallic nickel or the catalyst of palladium selected from load.Load hydrogenation catalyst can select preformed catalyst that powder can also be selected to urge Agent, catalyst carrier can be selected from aluminium oxide, silica gel and activated carbon.The load capacity of metallic nickel or palladium is selected from 0.3 ~ 10 weight %. Hydrogenation reactor can be selected from tank reactor and fixed bed reactors as required.
According to the present invention, polymer glue hydroconversion condition can select according to polymer property and hydrogenation catalyst type Select, do not make specified otherwise at this.
According to the present invention, polymer glue hydrogenation needs to separate hydrogenation catalyst to obtain the molten of described vistanex Liquid, concrete separate mode can select according to practical situation.If hydrogenation catalyst is fine catalyst, can select The mode of heat filtering separates;If hydrogenation catalyst is preformed catalyst, then can install in hydrogenation reactor exit Defecator carries out catalyst separation.The present invention is not required for concrete separate mode.
According to the present invention, described vistanex solution i.e. can get described vistanex through devolatilization separation solvent.
According to one further embodiment of the present invention, relate to a kind of moulded products, it be by melt-processed this Bright aforesaid vistanex is also molded with.As described forming method, such as can enumerate conventionally known in the art Any method, such as extrudes, is molded, rotational moulding and molded etc., the most preferred single or double screw extrusion molding.As described list Or the condition of molding of twin-screw extrusion molding, there is no particular limitation, can directly be suitable for commonly used in the art those, than As can be extruder barrel temperature at 150 DEG C-220 DEG C, die head temperature at 200 DEG C-220 DEG C, hauling speed 80-150cm/ Min, preferably 100-120cm/min, but it is not limited to this.Or, as the example of described rotation molding, such as can will be polymerized Compositions is put in rotational moulding container, the method carrying out rotational moulding at mould temperature 150-300 DEG C, and now molding cycle condition is: add The 5-30 minute time of heat, flatten 1--20 minute time, 1-20 minute cool time, but be not limited to this.
According to the present invention, the form of described moulded products is not particularly limited, can be such as thin film, sheet material, container (bucket, dish, bottle etc.), tubing, section bar etc..
Hereinafter use embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiments.
The molecular weight distribution mw/mn of vistanex measures: use the GPC V2000 type gel color of WATERS company of the U.S. Spectrometer is measured, and selects 4 Agilent PLgel Olexis type chromatographic columns, and with 1,2,4-trichloro-benzenes are flowing phase, Temperature during mensuration is 150 DEG C.
The density measurement of vistanex: reference standard GB/T 1033-86 carries out that (unit is g/cm3).
The bromine number of vistanex measures: reference standard GB11135-2008 is carried out, unit gBr/100g.
The determination of ash of vistanex: reference standard GB/T 9345.1-2008 is carried out, unit ppm(weight).
Embodiment 1
In 5L rustless steel polymeric kettle, add 2.0L hexane and 200g1,3-butadiene, in still, add 2mol/L's at normal temperatures The hexane solution 2.0mL of n-BuLi, is warming up to 70 DEG C and keeps 2h.Reaction terminates rear cooling discharge and obtains polymer glue.
Adding 200g deionized water in polymer glue, stand after being sufficiently stirred for 10min, layering takes upper organic phase and obtains To demetallated polymer glue.
Above-mentioned demetallated polymer glue is joined in 5L hydrogenation reaction kettle, adds 4g and load the powder palladium carbon of 5% palladium Catalyst, at hydrogen partial pressure 3.0MPa, is hydrogenated with 6h under the conditions of 150 DEG C.
Being separated with powder palladium carbon by polymer solution by heat filtering mode, then devolatilization pelletize obtains vistanex 1.
Embodiment 2
In 5L rustless steel polymeric kettle, add 2.0L oxolane and 200g1,3-butadiene, add in still at normal temperatures The hexane solution 10.0mL of the tert-butyl lithium of 2mol/L, is warming up to 70 DEG C and keeps 2h.Reaction terminates rear cooling discharge and is gathered Compound glue.
Adding 200g deionized water in polymer glue, stand after being sufficiently stirred for 20min, layering takes upper organic phase and obtains To demetallated polymer glue.
Joining in 5L hydrogenation reaction kettle by above-mentioned demetallated polymer glue, adding 3g palladium content is the neutrality of 0.5% Alumina load palladium catalyst powder, at hydrogen partial pressure 4.0MPa, is hydrogenated with 4h under the conditions of 170 DEG C.
Being separated with hydrogenation catalyst by polymer solution by heat filtering mode, then devolatilization pelletize obtains vistanex 2。
Embodiment 3
In 200L rustless steel polymeric kettle, add 100L heptane and 20kg isoprene, in still, add 1mol/L's at normal temperatures The hexane solution 0.2L of phenyl lithium, is warming up to 65 DEG C and keeps 3h.Reaction terminates rear cooling discharge and obtains polymer glue.
Adding 5kg deionized water in polymer glue, stand after being sufficiently stirred for 30min, layering takes upper organic phase and obtains To demetallated polymer glue.
By above-mentioned demetallated polymer glue by carrying out hydrogenation reaction in fixed bed reactors, fixed bed reactors fill Neutral silica gel is had to load the eggshell type supported catalyst of 0.5% Metal Palladium, Hydrogen Vapor Pressure 4.5Mpa, hydrogenation temperature 140 DEG C, air speed 0.6h-1, hydrogen-oil ratio is 200:1.
The polymer solution devolatization pelletize flowed out by above-mentioned hydrogenation reactor obtains vistanex 3.
Embodiment 4
Embodiment 3 is essentially identical, but is with the following changes:
Polymerization monomer is 10Kg1,3-butadiene and 10Kg isoprene, adds isoamyl two after 1,3-butadiene polymerization 1.5h Alkene, then repolymerization 1.5h;Polymerization initiator is the benzyl lithium n-heptane solution of 2.2mol/L, and consumption is 300mL.
Resulting polymers is designated as vistanex 4.
From table 1, vistanex of the present invention has extraordinary monodispersity (PDI of resin is respectively less than 1.5);And Vistanex has low-down content of ashes (ash is less than 10ppm).The preparation method of the vistanex of the present invention is to tree The molecular weight of fat has extraordinary regulating power.

Claims (7)

1. a vistanex, it is characterised in that there is the monomeric unit of derived from ethylene and derived from selected from propylene, butylene Or the monomeric unit of at least one alpha-olefin of Methyl-1-pentene, described vistanex is polymer, polydispersity coefficient PDI is less than 1.5, and the content of ashes of polymer is less than 10ppm.
Vistanex the most according to claim 1, it is characterised in that described density polymer is 0.88 ~ 0.98g/cm3, Polymer molecular weight is adjustable in the range of 1000 ~ 200000, the monomer list of described derived from propylene, butylene and Methyl-1-pentene The content of unit is 0.2 ~ 20 weight %.
3. the preparation method of a vistanex according to claim 1, it is characterised in that step includes:
In atent solvent, the anion of 1,3-butadiene or isoprene is caused with the organic compound of lithium metal or metallic sodium Polymerization prepares polymer glue;
Metal in removing polymer glue;
Spent hydroprocessing catalyst carries out catalytic hydrogenation and produces olefin polymer polymer glue;With
Described olefin polymer is obtained after separating hydrogenation catalyst and solvent.
The preparation method of vistanex the most according to claim 3, it is characterised in that described lithium metal or metallic sodium Organic compound is selected from lithium or the alkyl or aryl compound of sodium, preferably is selected from n-BuLi, isobutyl group lithium, tert-butyl lithium, phenyl Lithium and benzyl lithium, more preferably from n-BuLi, isobutyl group lithium and tert-butyl lithium.
The preparation method of vistanex the most according to claim 3, it is characterised in that described atent solvent refers to gold Belong to lithium or the organic compound of metallic sodium and 1,3-butadiene or isoprene does not has chemically active solvent, preferably be selected from penta Alkane, hexane, hexamethylene, heptane and oxolane or two of which or the combination of two or more solvent, more preferably from hexane, hexamethylene Alkane and oxolane or the combination of two of which solvent.
The preparation method of vistanex the most according to claim 3, it is characterised in that described hydrogenation catalyst is selected from negative The metallic nickel of loadization or the catalyst of palladium.
7. a moulded products, it is characterised in that by melt-processed according to the polyolefin tree described in any one of claim 1-3 Fat molding and manufacture.
CN201610631922.1A 2016-08-04 2016-08-04 A kind of vistanex and preparation method and application Pending CN106243258A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1089272A (en) * 1992-12-26 1994-07-13 中国石油化工总公司 The method of contents of ethylene in control dienite and the multipolymer
US6228908B1 (en) * 1997-07-11 2001-05-08 Bridgestone Corporation Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds
US6562923B1 (en) * 2000-09-11 2003-05-13 Michelin Recherche Et Technique S.A. Process for the preparation of a dilithiated initiator and anionic polymerization process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1089272A (en) * 1992-12-26 1994-07-13 中国石油化工总公司 The method of contents of ethylene in control dienite and the multipolymer
US6228908B1 (en) * 1997-07-11 2001-05-08 Bridgestone Corporation Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds
US6562923B1 (en) * 2000-09-11 2003-05-13 Michelin Recherche Et Technique S.A. Process for the preparation of a dilithiated initiator and anionic polymerization process

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
张小舟,等: "《高分子化学》", 31 January 2015, 哈尔滨工业大学出版社 *
王久芬,等: "《高聚物合成工艺》", 31 January 2013, 国防工业出版社 *
高阳峰,等: "窄分布液体聚丁二烯的聚合动力学及加氢效果", 《石油化工》 *
魏荣宝,等: "《有机化学》", 31 August 2003, 天津大学出版社 *

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Application publication date: 20161221