CN106117405A - A kind of preparation method of the low-ash vistanex of single dispersing - Google Patents
A kind of preparation method of the low-ash vistanex of single dispersing Download PDFInfo
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- CN106117405A CN106117405A CN201610631785.1A CN201610631785A CN106117405A CN 106117405 A CN106117405 A CN 106117405A CN 201610631785 A CN201610631785 A CN 201610631785A CN 106117405 A CN106117405 A CN 106117405A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers 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
- C08F236/04—Copolymers 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
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; 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
- C08F4/46—Metals; 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
- C08F4/48—Metals; 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses the preparation method of the low-ash vistanex of a kind of single dispersing, comprising the following steps: cause starting monomer 1 in atent solvent with the organic compound of lithium metal or metallic sodium, the anionic polymerisation of 3 butadiene or isoprene 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 the step by hydrogenated products with olefin polymer described in hydrogenation catalyst and solvent isolated.The preparation method technique simple possible of the vistanex of the present invention, is suitable for commercial production.The method of the present invention has good regulating power to the molecular weight of resin.The monodispersity using the vistanex of the method manufacture 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.
Description
Technical field
The present invention relates to the manufacture method of a kind of vistanex.Specifically, the present invention relates to have monodispersity and
The manufacture method of the low-down vistanex of content of ashes.
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 can also 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 the manufacturing technology of a kind of vistanex, and its product manufactured has
Monodispersity and low content of ashes, it is possible to more preferably embody the performance of polyolefin itself.
Summary of the invention
The present inventor finds through diligent research on the basis of existing technology, by using the one specifically side of preparation
Method manufactures vistanex, it is possible to solves foregoing problems, and this completes the present invention.
The preparation method of the low-ash vistanex of a kind of single dispersing, comprises the following steps:
In atent solvent, starting monomer 1,3-butadiene or isoprene is caused with the organic compound of lithium metal or metallic sodium
Anionic polymerisation prepare 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 hydrogenation catalyst and solvent isolated.
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 and 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.
Described starting monomer 1,3-butadiene and isoprene concentration in atent solvent by reactor remove heat energy power and
The restriction of polymerization temperature, selected from 5 ~ 30 weight %, preferably is selected from 10 ~ 20 weight %.
The organic compound of described lithium or sodium and the mol ratio of starting monomer are selected from 20:1 ~ 4000:1.
The polymerization temperature of described starting monomer is selected from 40 ~ 100 DEG C, and polymerization time is selected from 0.2 ~ 4h.
The polymerization temperature of described starting monomer preferably is selected from 50 ~ 70 DEG C, and polymerization time preferably is selected from 0.5 ~ 2h.
Beneficial effects of the present invention:
The preparation method technique simple possible of the vistanex of the present invention, is suitable for commercial production.The method of the present invention is to tree
The molecular weight of fat has good regulating power.
The monodispersity using the vistanex of the method manufacture of the present invention is good, can give full play to the property of vistanex
Energy.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 product transparency, insulating properties
With the product that there is particular/special requirement in the life-span etc., such as battery membranes etc..It also is suitable as additive to add in other polyolefine material
Enhance product performance.
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.
According to the present invention, the manufacture method of described vistanex is to be passed through anion by 1,3-butadiene or isoprene
After polymerization, then demetalization is hydrogenated with manufacture.
Specifically, the present invention relates to the manufacture 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 or 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 or the organic compound of metallic sodium, this metallo-organic compound has Anionic Polymerization Living, selected from lithium or 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 the present invention, the form of described moulded products is not particularly limited, such as can enumerate thin film, sheet material, appearance
Device (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 (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, use the vistanex of method manufacture of the present invention have extraordinary monodispersity (resin
PDI is respectively less than 1.5)；And vistanex has low-down content of ashes (ash is less than 10ppm).The polyolefin tree of the present invention
The preparation method of fat has extraordinary regulating power to the molecular weight of resin.The manufacture method of vistanex of the present invention
Simple possible, is suitable for and commercial production.
Claims (9)
1. the preparation method of the low-ash vistanex of single dispersing, it is characterised in that comprise the following steps:
In atent solvent, starting monomer 1,3-butadiene or isoprene is caused with the organic compound of lithium metal or metallic sodium
Anionic polymerisation prepare 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 hydrogenation catalyst and solvent isolated.
2. according to the preparation method of the vistanex described in claim 1, 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.
3. according to the preparation method of the vistanex described in claim 1, it is characterised in that described atent solvent refers to gold
Belong to lithium and 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.
4. according to the preparation method of the vistanex described in claim 1, it is characterised in that described hydrogenation catalyst is selected from negative
The metallic nickel of loadization or the catalyst of palladium.
5. according to the preparation method of the vistanex described in claim 1, it is characterised in that
Described starting monomer 1,3-butadiene and isoprene concentration in atent solvent are removed heat energy power and polymerization by reactor
The restriction of temperature, selected from 5 ~ 30 weight %.
6. according to the preparation method of the vistanex described in claim 5, it is characterised in that preferably be selected from 10 ~ 20 weight %.
7. according to the preparation method of the vistanex described in claim 1, it is characterised in that described lithium or the organic compound of sodium
Thing is selected from 20:1 ~ 4000:1 with the mol ratio of starting monomer.
8. according to the preparation method of the vistanex described in claim 1, it is characterised in that the polymerization temperature of described starting monomer
Degree is selected from 40 ~ 100 DEG C, and polymerization time is selected from 0.2 ~ 4h.
9. according to the preparation method of the vistanex described in claim 8, it is characterised in that the polymerization temperature of described starting monomer
Degree preferably is selected from 50 ~ 70 DEG C, and polymerization time preferably is selected from 0.5 ~ 2h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667074A (en) * | 2021-09-14 | 2021-11-19 | 郭方飞 | Industrial production device and production method for medical-grade thermoplastic elastomer |
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|---|---|---|---|---|
| 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 |
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2016
- 2016-08-04 CN CN201610631785.1A patent/CN106117405A/en active Pending
Patent Citations (3)
| 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 |
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| Title |
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| 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: "《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》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667074A (en) * | 2021-09-14 | 2021-11-19 | 郭方飞 | Industrial production device and production method for medical-grade thermoplastic elastomer |
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