CN105968243B - A kind of preparation method of polyisoprene catalyst - Google Patents

A kind of preparation method of polyisoprene catalyst Download PDF

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CN105968243B
CN105968243B CN201610386752.5A CN201610386752A CN105968243B CN 105968243 B CN105968243 B CN 105968243B CN 201610386752 A CN201610386752 A CN 201610386752A CN 105968243 B CN105968243 B CN 105968243B
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catalyst
parts
cyclopentadiene
polyisoprene
preparation
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CN105968243A (en
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王琪宇
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Wuhan Penglei Biotechnology Co ltd
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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
    • C08F136/08Isoprene
    • 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
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F4/60Metals; 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 together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70Iron group metals, platinum group metals or compounds thereof

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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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A kind of preparation method of polyisoprene catalyst:In a kettle, methyl acrylate is added, diallyl phthalate, ferrocene, bis- (three carbonyl cyclopentadiene molybdenums), three rhenium carbonyl of cyclopentadiene, three (isopropoxy cyclopentadiene) ceriums, reacts under preference temperature, obtained product obtains catalyst prod through filtering after drying.

Description

A kind of preparation method of polyisoprene catalyst
Technical field
The present invention relates to a kind of preparation method of catalyst, especially a kind of preparation method of polyisoprene catalyst.
Background technology
The polymerization of cis- Isosorbide-5-Nitrae-polyisoprene, industrial production is generally using two kinds of catalyst system and catalyzings in the world:TiCl4-AlR3 The ziegler-natta catalyzed system and butyl lithium catalyst of composition.Rare-earth catalysis system has been developed in China.① TiCl4- AlR3 systems:Industrially common triisobutyl aluminium (i.e. R is isobutyl group).Make solvent with low boiling hydrocarbon.Trace impurity such as ring penta 2 Alkene and carboxyl compound have certain influence to polymerization process and polymer property.Al/Ti molar ratios, catalyst preparation method and Polymerizing condition influences catalytic activity and polymer property notable.The compounds such as third component such as ether, amine, ketone are commonly incorporated into, to carry High catalytic activity, cis--content of Isosorbide-5-Nitrae structure, molecular weight, Mooney viscosity, and reduce gel etc..Cis- -1,4 structure contains Amount is up to 97%.2. butyl lithium catalyst:Feature is that the molecular weight and molecualr weight distribution of polymer is controllable;Catalyst amount It is few;But to micro amount of oxygen, water and some are oxygen-containing, nitrogenous compound is very sensitive, therefore very harsh to the purity requirement of raw material. The content of cis-structure is no more than 93% in product, and performance is poor compared with the rubber that titanium catalyst produces.Therefore, it and has developed many and changes The lithium catalyst of property.3. rare earth catalyst:Make isoprene polymerization with rare earth catalyst in hydrogasoline, can be made it is cis-- Polymer of the Isosorbide-5-Nitrae structural content up to 96%, microstructure are not easy to be influenced by polymerizing condition.Catalyst amount is compared with titanium catalyst Few, gel content is also less.
CN103254332A discloses a kind of preparation method of polyisoprene and is prepared by this method poly- different Pentadiene, this method are included under solution polymerization condition, make the mixture containing isoprene monomer, catalyst and organic solvent In isoprene monomer polymerization, obtain polyisoprene solution, the catalyst contains halogenated titanium and organo-aluminum compound, In, this method further includes that the polyisoprene solution that will be obtained is contacted with oleic acid, and by the aqueous solution of the hydroxide of alkali metal And/or the aqueous solution of the hydroxide of alkaline-earth metal with polyisoprene solution is contacted with oleic acid after obtained solution mix, And carry out water-oil separating.
CN101045768 discloses a kind of rare earth catalyst preparing polyisoprene and preparation method and prepares polyisoprene Method.The composition of the catalyst is carboxylic acid neodymium, alkyl aluminum, chloride, conjugated diolefin, and proportioning is alkyl aluminum: chloride: Conjugated diolefin: carboxylic acid neodymium 5-30: 1.0-4.0: 5-20: 1, the present invention can obtain the rare earth catalyst of homogeneous stability.It should Catalyst has higher catalytic activity, causes isoprene polymerization under higher polymerization temperature, obtains high cis- 1,4 knot Structure content (>=96%) and narrow molecular weight distribution (<3.0) and with stretch crystallization performance characteristics polyisoprene.
Polyisoprene catalyst in the prior art mainly uses liquid phase to mix, and has and is easy to run off, cannot reuse The shortcomings that, affect the using effect of catalyst.
Invention content
Above-mentioned technical problem present in present invention aims to solve the prior art provides a kind of polyisoprene catalysis The preparation method of agent, it is characterised in that preparation process includes:
In a kettle, 100 parts of methyl acrylates, 10-30 parts of diallyl phthalates, 1- are added by weight 10 parts of ferrocene, 1-10 parts bis- (three carbonyl cyclopentadiene molybdenums), 1-5 parts of three rhenium carbonyls of cyclopentadiene, three (isopropyl of 0.1-0.5 parts Oxygroup cyclopentadiene) cerium, 1000-3000 parts of water, 1-4 parts of polyvinyl alcohol, 0.5-2 parts of benzoyl peroxides, at 80 DEG C -95 DEG C 5-12h is reacted, filtering obtains catalyst prod after drying.
The methyl acrylate, diallyl phthalate;Ferrocene is commercial product;Bis- (three carbonyl rings penta 2 Alkene molybdenum) it is commercial product, the product produced such as Shanghai Jiang Lai Science and Technology Ltd.s;Three rhenium carbonyl of cyclopentadiene is commercial product, As the product of the limited public production of auspicious chemical technology is pushed up in Shanghai;Three (isopropoxy cyclopentadiene) ceriums are commercial product, such as Shenzhen Five products produced up to instrument firm with perseverance.
Compared with prior art, catalyst and preparation method thereof of the invention, has the advantages that:
Iron, molybdenum, rhenium, the metals such as cerium and rare earth element are introduced on its skeleton of methacrylate resin, improving catalyst makes It with the service life, remains to keep higher catalytic activity by long-play, reusable, 10 polymer yields of Reusability 98% or more highest.
Specific implementation mode
Following instance is only to further illustrate the present invention, and is not limitation the scope of protection of the invention.
Embodiment 1:
In 5000L reaction kettles, addition 100Kg methyl acrylates, 20Kg diallyl phthalates, 5Kg ferrocene, 5Kg bis- (three carbonyl cyclopentadiene molybdenums), three rhenium carbonyl of 3Kg cyclopentadiene, 0.3Kg tri- (isopropoxy cyclopentadiene) cerium, 2000Kg water, 2Kg polyvinyl alcohol, 1.5Kg benzoyl peroxides react 8h at 90 DEG C, and filtering obtains catalyst production after drying Product.Number is M-1.
Embodiment 2:
In 5000L reaction kettles, addition 100Kg methyl acrylates, 10Kg diallyl phthalates, 1Kg ferrocene, 1Kg bis- (three carbonyl cyclopentadiene molybdenums), three rhenium carbonyl of 1Kg cyclopentadiene, 0.1Kg tri- (isopropoxy cyclopentadiene) cerium, 1000Kg water, 1Kg polyvinyl alcohol, 0.5Kg benzoyl peroxides react 5h at 80 DEG C, and filtering obtains catalyst production after drying Product.Number is M-2.
Embodiment 3
In 5000L reaction kettles, 100Kg methyl acrylates, 30Kg diallyl phthalates, bis- cyclopentadienyls of 10Kg is added Iron, 10Kg bis- (three carbonyl cyclopentadiene molybdenums), three rhenium carbonyl of 5Kg cyclopentadiene, 0.5Kg tri- (isopropoxy cyclopentadiene) cerium , 3000Kg water, 4Kg polyvinyl alcohol, 2Kg benzoyl peroxides, at 95 DEG C react 5h, filtering, obtained after drying catalyst production Product.Number is M-3.
Comparative example 1
It is added without ferrocene, the other the same as in Example 1.Number is M-4.
Comparative example 2
It is added without bis- (three carbonyl cyclopentadiene molybdenums), the other the same as in Example 1.Number is M-5.
Comparative example 3
It is added without three rhenium carbonyl of cyclopentadiene, the other the same as in Example 1.Number is M-6.
Comparative example 4
It is added without three (isopropoxy cyclopentadiene) ceriums, the other the same as in Example 1.Number is M-7.
Embodiment 4
Catalyst 0.05L, the 0.4L solvent naphtha prepared by embodiment 1-3 and comparative example 1-4 is added in 1L reactors, 0.1L isoprene monomers, 48 DEG C of reaction temperature, reaction terminate for 5 hours, and product passes through gas chromatographic detection, calculates polymer Yield.
Table 1:Catalyst Reusability 10 times, the yield of polymer:
Number The yield % of polyisoprene
M-1 96
M-2 95
M-3 98
M-4 91
M-5 91
M-6 88
M-7 87
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made simple change, etc. With replacement or modification etc., all it is covered by among protection scope of the present invention.

Claims (1)

1. a kind of preparation method of polyisoprene catalyst, it is characterised in that include the following steps:
In a kettle, 100 parts of methyl acrylates, 10-30 portions of diallyl phthalates, 1-10 parts are added by weight Ferrocene, 1-10 parts bis- (three carbonyl cyclopentadiene molybdenums), 1-5 parts of three rhenium carbonyls of cyclopentadiene, three (isopropyl oxygen of 0.1-0.5 parts Butylcyclopentadiene) cerium, 1000-3000 parts of water, 1-4 parts of polyvinyl alcohol, 0.5-2 parts of benzoyl peroxides, instead at 80 DEG C -95 DEG C 5-12h is answered, filters, catalyst prod is obtained after drying.
CN201610386752.5A 2016-06-05 2016-06-05 A kind of preparation method of polyisoprene catalyst Active CN105968243B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1225925A (en) * 1998-02-12 1999-08-18 华东理工大学 Efficient catalyst for olefin polymerization process
CN102010476B (en) * 2010-11-02 2012-07-11 江南大学 Method for preparing monodisperse polymer microsphere by irradiation polymerization of ultraviolet light
CN102911298B (en) * 2011-08-03 2014-10-15 中国石油化工集团公司 Catalyzing system for isoprene polymerization and preparation and application method of catalyzing system
CN103289000B (en) * 2013-07-01 2015-09-02 青岛科技大学 A kind of High molecular weight polyisoprene rubber and preparation method thereof
CN103819618A (en) * 2014-02-12 2014-05-28 中国科学院长春应用化学研究所 Preparation method of ethylene-propylene-polyisoprene copolymer
CN104801312B (en) * 2015-03-17 2017-07-07 烟台大学 A kind of composite oxide catalysts and preparation method
CN105504566B (en) * 2016-01-26 2018-01-16 西南科技大学 A kind of preparation method of column styrene divinylbenzene copolymer hydrophobic catalyst carrier

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