CN106046226A - Diene polymer and preparation method thereof - Google Patents
Diene polymer and preparation method thereof Download PDFInfo
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- CN106046226A CN106046226A CN201610348812.4A CN201610348812A CN106046226A CN 106046226 A CN106046226 A CN 106046226A CN 201610348812 A CN201610348812 A CN 201610348812A CN 106046226 A CN106046226 A CN 106046226A
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- rare earth
- diolefin
- alkyl aluminum
- compound
- age resistor
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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
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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
- C08F136/08—Isoprene
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- Polymers & Plastics (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
The invention provides a preparation method of a diene polymer. The method comprises the following steps: a rare earth catalyst, an alkyl aluminum modified anti-aging agent and diene are mixed; and polymerization is carried out, such that the diene polymer is obtained. According to the invention, the alkyl aluminum modified anti-aging agent is added during diene polymerization, such that the alkyl aluminum modified anti-aging agent participates the polymerization of diene. Therefore, the small-molecular anti-aging agent is connected with high-molecular chains. Problems of small-molecular anti-aging agent vulnerabilities to volatilization, migration and extraction are effectively avoided, and rubber anti-oxidation and anti-aging performances are improved. Also, rubber and the small-molecular anti-aging agent are connected through a manner of chemical bond, such that the anti-aging agent can be more easily dispersed in the high-molecular material substrate. Therefore, the anti-oxidation and anti-aging performances of rubber are further improved. As a result of experiments, the anti-aging performance of rubber prepared with the method provided by the invention is substantially better than the anti-aging performance of commercially available products of which the anti-aging agent is mixed in rubber in a physical way.
Description
Technical field
The invention belongs to polymer synthesis techniques field, particularly relate to a kind of double olefin copolymer and preparation method thereof.
Background technology
Rubber and rubber are in the middle of the process of storage and use, in order to suppress or delay due to by environment
Heat and air in the effect of oxygen and the catabiosis that occurs, need the chemical assistant adding a certain amount of inhibitory action the most anti-
Oxygen agent or age resistor, extend the service life of rubber and its goods, improves their use value.
Industrial conventional antioxidant or age resistor include Hinered phenols, arylamine class, containing Phosphorus and sulfur-bearing class etc., Qi Zhongshou
Resistance phenol and arylamine are maximally effective two class primary antioxidants, apply relatively broad in rubber industry.Antioxidant is directly added into rubber
In matrix, although can effectively prevent rubber deterioration by oxidation, but little molecule antioxidant in rubber matrix for physically dispersion or
Mixing, and most of rubber is nonpolar or low polarity macromolecule, and the compatibility with little molecule antioxidant is poor, causes little point
Sub-antioxidant easily migrates from matrix, extracts out and lose so that the ability of rubber opposing thermo-oxidative ageing declines, and is unfavorable for that it is long-term
Store, affect the mechanical property of rubber simultaneously, and little molecule antioxidant migrates or is retracted in natural environment, the body to people
Body health causes serious impact.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of double olefin copolymer and preparation method thereof, the present invention provides
Double olefin copolymer there is preferable ageing resistace.
The invention provides the preparation method of a kind of double olefin copolymer, comprise the following steps:
Rare earth catalyst, alkyl aluminum modification age resistor and diolefin are mixed, is polymerized, obtains double olefin copolymer.
Preferably, described rare earth catalyst is by including rare earth compound, the first diolefin, alkyl aluminum compound and chloride
Make；
The preparation process of described double olefin copolymer specifically includes:
A1) rare earth compound, the first diolefin, alkyl aluminum compound and chloride are mixed, be aged, obtain rare earth
Catalyst；
B1) described rare earth catalyst, alkyl aluminum modification age resistor and the second diolefin are mixed, be polymerized, obtain double
Olefin polymer；
Described first diolefin and the second diolefin are independently selected from butadiene or isoprene.
Preferably, described rare earth catalyst is by including that rare earth compound, the first diolefin and muriatic mixture are made；
The preparation process of described double olefin copolymer specifically includes:
A2) rare earth compound, the first diolefin, alkyl aluminum modification age resistor and chloride are mixed, be aged, obtain
Rare earth catalyst；
B2) described rare earth catalyst and the second diolefin are mixed, be polymerized, obtain double olefin copolymer；
Described first diolefin and the second diolefin are independently selected from butadiene or isoprene.
Preferably, described alkyl aluminum modification age resistor prepares according to following steps:
Alkyl aluminum compound and age resistor are mixed, reacts, obtain the age resistor that alkyl aluminum is modified.
Preferably, when preparing alkyl aluminum modification age resistor, described alkyl aluminum compound includes trialkylaluminium and/or alkyl hydrogen
Change aluminum；
Described age resistor include phenol antiager, virtue amines antioxidants, containing in Phosphorus age resistor and sulfur-bearing class age resistor
One or more；
The mol ratio of described alkyl aluminum compound and age resistor is (1～10): 1.
Preferably, described rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphonate, alkane
One or more in epoxide rare earth and rare earth chloride electron donor coordination compound；
Rare earth element in described rare earth compound includes one or more in neodymium, lanthanum and shirt.
Preferably, described chloride include a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, sesquialter aluminium ethide, tertiary butyl chloride,
One in benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane and Silicon chloride. or
Several.
Preferably, described step A1) in the rubbing of rare earth compound, alkyl aluminum compound, chloride and the first diolefin
That ratio is 1:(5～30): (1～3): (5～20)；
Described step B1) in the molal quantity of rare earth catalyst rare earth elements and the mass ratio of the second diolefin be (1
×10-6～6 × 10-6) mol:1g；
Described step B1) in alkyl aluminum modification age resistor and the mass ratio of the second diolefin be (0.5～2): 1000.
Preferably, described step A2) in rare earth compound, alkyl aluminum modification age resistor, chloride and the first diolefin
Mol ratio be 1:(5～40): (1～3): (5～20)；
Described step B2) in the molal quantity of rare earth catalyst rare earth elements and the mass ratio of the second diolefin be (1
×10-6～6 × 10-6) mol:1g.
The present invention provides a kind of double olefin copolymer, the preparation method described in claim 1～9 any one prepare.
The invention provides the preparation method of a kind of double olefin copolymer, comprise the following steps: by rare earth catalyst, alkyl
Aluminum modification age resistor and diolefin mixing, be polymerized, obtain double olefin copolymer.Alkyl aluminum modification age resistor is existed by the present invention
Add the when of diolefin polymerization, participate in the polymerization of diolefin, make to be connected, so between little molecule age resistor and macromolecular chain
Be not only able to be prevented effectively from the migration volatile, easy of little molecule age resistor and the easy problem such as extraction, improve rubber self antioxidation,
Aging-resistant performance；Being additionally, since between rubber and little molecule age resistor is to be connected by the way of chemical bond so that anti-old
Agent is easier to dispersion in macromolecular material matrix, further increases the antioxidation of rubber self, aging-resistant performance.Experiment
Result shows, the ageing resistace age resistor to be substantially better than of rubber self prepared according to the method in the present invention is with physics shape
The ageing resistace of the commercially available prod that formula is blended in rubber.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to
The accompanying drawing provided obtains other accompanying drawing.
Fig. 1 is polybutadiene ageing time test curve in the embodiment of the present invention and comparative example；
Fig. 2 is polyisoprene ageing time test curve in the embodiment of the present invention and comparative example.
Detailed description of the invention
The invention provides the preparation method of a kind of double olefin copolymer, comprise the following steps:
Rare earth catalyst, alkyl aluminum modification age resistor and diolefin are mixed, is polymerized, obtains double olefin copolymer.
The age resistor that alkyl aluminum is modified is added diolefin polymerization when by the present invention, participates in polymerization, makes little molecule prevent
It is connected between old agent and macromolecular chain, not only improves the antioxidation of rubber self, aging-resistant performance, and can effectively keep away
Exempt from the problem such as the migration volatile, easy of little molecule age resistor and easy extraction.
Wherein, the age resistor that described alkyl aluminum is modified can add preparing rare earth catalyst when, it is also possible to double
The polymerization process of alkene adds.
Adding fashionable when described alkyl-modified age resistor is at diolefin polymerization when, described rare earth catalyst includes rare earth
Compound, the first diolefin, alkyl aluminum compound and chloride, the present invention preferably prepares diolefin according to following steps and gathers
Compound:
Rare earth compound, the first diolefin, alkyl aluminum compound and chloride are mixed, is aged, obtains first dilute
Soil catalyst (in order to distinguish with rare earth catalyst below, urged by the present invention by named for rare earth catalyst herein the first rare earth
Agent)；
By described first rare earth catalyst, the age resistor of alkyl aluminum modification and the mixing of the second diolefin, it is polymerized, obtains
Double olefin copolymer.
Rare earth compound, the first diolefin, alkyl aluminum compound and chloride are mixed by the present invention, are aged, obtain
First rare earth catalyst, rare earth compound, the first diolefin and alkyl aluminum compound are the most first mixed, carry out old by the present invention
Change, then add chloride, be aged, obtain the first rare earth catalyst.
In the present invention, described rare earth compound preferably includes rare earth carboxylate, rare earth superphosphate, rare earth acidity phosphine
One or more in hydrochlorate, alkoxy rare-earth and rare earth chloride electron donor coordination compound, more preferably include neodymium caprate Nd
(vers)3, neodymium iso-octanate Nd (EHA)3, neodymium naphthenate Nd (naph)3, (2-ethylhexyl) acid neodymium Nd (P204)3, (2-ethyl hexyl
Base) phosphonic acids neodymium list-2-ethylhexyl ester Nd (P507)3, ethyoxyl neodymium, positive propoxy neodymium, isopropoxy neodymium, isobutoxy neodymium, tertiary fourth
Epoxide neodymium, different octyloxy neodymium, Neodymium chloride isopropanol (NdCl3·3PriAnd Neodymium chloride tributyl phosphate (NdCl OH)3In 3TBP)
One or more；Described first diolefin includes butadiene or isoprene；Described alkyl aluminum preferably include trialkylaluminium and/
Or alkyl-al hydride, more preferably include triisobutyl aluminium (Al (i-Bu)3), diisobutylaluminium hydride (Al (i-Bu)2H), diethyl
Aluminum hydride (AlEt2H), trioctylaluminum (Al (oct)3) and triethyl aluminum (AlEt3One or more in)；Described chloride is excellent
Choosing includes a chloro-di-isobutyl aluminum (Al (i-Bu)2Cl), aluminium diethyl monochloride (AlEt2Cl), sesquialter aluminium ethide (Al2Et3Cl3),
Tertiary butyl chloride (t-BuCl), benzyl chloride (BzCl), allyl chloride (H2C=CHCH2Cl), chloromethyl silane Me4-nSiCln(n is
1,2 or 3) and Silicon chloride. (SiCl4One or more in).
In the present invention, the mol ratio of described rare earth compound and alkyl aluminum compound is preferably 1:(5～30), more preferably
For 1:(15～25), concrete, in an embodiment of the present invention, can be 1:15,1:20 or 1:25；Described rare earth compound and
Muriatic mol ratio is preferably 1:(1～3), more preferably 1:2；The mol ratio of described rare earth compound and the first diolefin is excellent
Elect 1:(5～20 as), more preferably 1:(10～15), concrete, in an embodiment of the present invention, 1:10 or 1 can be used:
20。
In the present invention, the temperature of the ageing of described rare earth compound, the first diolefin and alkyl aluminum compound is preferably 0
～80 DEG C, preferably 20～60 DEG C, most preferably 30～50 DEG C；Described rare earth compound, the first diolefin and alkyl aluminum chemical combination
The time of the ageing of thing is preferably 5～30min, more preferably 10～25min, most preferably 15～20min；After adding chloride
The temperature of ageing be preferably 0～80 DEG C, preferably 20～60 DEG C, most preferably 30～50 DEG C；Add the ageing after chloride
Time be preferably 5～60min, more preferably 10～50min, most preferably 20～40min, concrete, can be 30min.
The present invention preferably carries out the preparation of above-mentioned first rare earth catalyst under protective gas atmosphere, and described protective gas preferably wraps
Include nitrogen, argon or helium.
The present invention preferably by described rare earth compound, the first diolefin, alkyl aluminum compound and chloride respectively with organic
After solvent mixing, then by organic molten to the rare earth compound organic solution obtained, the first diolefin organic solution, alkyl aluminum compound
Liquid and chloride organic solution carry out above-mentioned reaction, prepare the first rare earth catalyst；Described organic solvent preferably include normal hexane,
One or more of pentane, hexamethylene and normal heptane.After being aged for the first time, the present invention is preferably old in described first time
Change in the mixture obtained and add organic solvent so that it is molar concentration is 2 × 10-5mol/mL。
After obtaining the first rare earth catalyst, the present invention by age resistor modified to described first rare earth catalyst, alkyl aluminum with
Second diolefin mixing, is polymerized, obtains double olefin copolymer.The most described second diolefin of the present invention mixes with organic solvent
After conjunction, then carrying out described polyreaction, described organic solvent preferably includes in normal hexane, pentane, hexamethylene and normal heptane
One or more.In the present invention, described second diolefin preferably includes butadiene or isoprene；The modification of described alkyl aluminum
Age resistor preferably prepares according to following steps:
Alkyl aluminum compound and age resistor are mixed, reacts, obtain the age resistor that alkyl aluminum is modified.
In the present invention, described alkyl aluminum compound preferably includes trialkylaluminium and/or alkyl-al hydride, more preferably includes
Triisobutyl aluminium (Al (i-Bu)3), diisobutylaluminium hydride (Al (i-Bu)2H), ADEH (AlEt2H), trioctylaluminum
(Al(oct)3) and triethyl aluminum (AlEt3One or more in)；Prepare the alkane that the modified age resistor of described alkyl aluminum is used
Alkyl aluminum compound used when preparing the first rare earth catalyst in base aluminium compound and technique scheme can identical also may be used
With difference, it is not particularly limited；Described age resistor preferably include phenol antiager, virtue amines antioxidants, containing Phosphorus age resistor and
One or more in sulfur-bearing class age resistor, more preferably include octylated diphenylamine, 4, double (alpha, alpha-dimethylbenzyl) hexichol of 4'-
Amine, N-isopropyl-N'-diphenyl-para-phenylene diamine, N-(1-methylheptyl)-N'-diphenyl-para-phenylene diamine, N, N'-diphenyl are to benzene two
Amine, N, N'-bis-(betanaphthyl) p-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-benzene
Base p-phenylenediamine, 2,6 di tert butyl 4 methyl phenol, styrenated phenol, 2,2' methylene bis (4-methyl-6-tert butyl
Phenol), 2,2' methylene bis (4 one ethyl-6-tert-butyl phenol), 4,4' butylidene bis (the 6-tert-butyl group-3-methylphenol)
With one or more in 4,4'-thiobis (the 6-tert-butyl group-3-methylphenol).In the present invention, described alkyl aluminum compound
It is preferably (1～10): 1 with the mol ratio of age resistor, more preferably (2～9): 1, concrete, can be 1:3,1:4,1:5 or 1:
8；The described reaction temperature preparing age resistor is preferably-20～30 DEG C, more preferably-10～20 DEG C, most preferably 0～10 DEG C.
In the present invention, the molal quantity of described first rare earth catalyst rare earth elements and the mass ratio of the second diolefin
It is preferably (1 × 10-6～6 × 10-6) mol:1g, more preferably (3 × 10-6～5 × 10-6) mol:1g；The modification of described alkyl aluminum
Age resistor is preferably (0.5～2) with the mass ratio of described second diolefin: 1000, more preferably (0.8～1.5): 1000.
In the present invention, the temperature of described polymerization is preferably 0～70 DEG C, more preferably 20～50 DEG C；Described polymerization time
Between be preferably 1～24 hour, more preferably 3～20 hours, concrete, can be 5 hours or 6 hours.
The present invention can also add the age resistor that alkyl aluminum is modified preparing the second rare earth catalyst when, will the most again
Having the second rare earth catalyst and the diolefin polymerization of alkyl aluminum modification age resistor, obtain double olefin copolymer, rare earth now is urged
Agent is by including that rare earth compound, the first diolefin and muriatic mixture are made, and concrete preparation process is as follows:
By rare earth compound, the first diolefin, the age resistor of alkyl aluminum modification and chloride mixing, it is aged, obtains
(in order to distinguish with above-mentioned first rare earth catalyst, the present invention is by named for rare earth catalyst herein for second rare earth catalyst
Two rare earth catalysts)；
Described second rare earth catalyst and the second diolefin are mixed, is polymerized, obtains double olefin copolymer；
The present invention, by rare earth compound, the first diolefin, the age resistor of alkyl aluminum modification and chloride mixing, carries out old
Changing, obtain the second rare earth catalyst, the present invention is the most first by rare earth compound, the first diolefin and the age resistor of alkyl aluminum modification
Mixing, is aged, then adds chloride, be aged, obtain the second rare earth catalyst.
The present invention is preferably by described rare earth compound, the first diolefin, the age resistor of alkyl aluminum modification and chloride respectively
After mixing with organic solvent, then by organic molten to the rare earth compound organic solution obtained, the first diolefin organic solution, alkyl aluminum
Liquid and chloride organic solution carry out above-mentioned reaction, prepare the first rare earth catalyst；Described organic solvent preferably include normal hexane,
One or more of pentane, hexamethylene and normal heptane.After being aged for the first time, the present invention is preferably old in described first time
Change in the mixture obtained and add organic solvent so that it is molar concentration is 2 × 10-5mol/mL。
In the present invention, described rare earth compound, the first diolefin and muriatic kind, consumption and source and above-mentioned skill
Art scheme middle rare earth compound, the first diolefin and muriatic kind, consumption are consistent with source, do not repeat them here.Described
The age resistor of alkyl aluminum modification is consistent with the preparation method of the age resistor of alkyl aluminum modification in technique scheme, the most superfluous at this
State.
In the present invention, described rare earth compound is preferably 1:(5～40 with the mol ratio of alkyl-modified age resistor), more
It is preferably 1:(10～35), concrete, in an embodiment of the present invention, can be 1:15 or 1:30.In the present invention, preparation the
The digestion time of twice ageing of two rare earth catalysts and Aging Temperature prepare the first rare earth catalyst in technique scheme
The digestion time of twice ageing consistent with Aging Temperature, do not repeat them here.
After obtaining the second rare earth catalyst, described second rare earth catalyst and the second diolefin are mixed by the present invention, carry out
Polymerization, obtains double olefin copolymer.In the present invention, the molal quantity of described first rare earth catalyst rare earth elements and second pair
The mass ratio of alkene is preferably (1 × 10-6～6 × 10-6) mol:1g, more preferably (3 × 10-6～5 × 10-6) mol:1g；?
In the present invention, the temperature of described polymerization is preferably 0～70 DEG C, more preferably 20～50 DEG C；The time of described polymerization be preferably 1～
24 hours, more preferably 3～20 hours, concrete, can be 5 hours or 6 hours.
The present invention is according to GB/T3512-2014 vulcanite or hot shortness's rubber hot-air accelerated ageing and heat resistant test side
Method tests the ageing resistace of double olefin copolymer in the present invention, and result shows, resisting of the double olefin copolymer in the application
Ageing properties is substantially better than commercially available commodity.
The invention provides the preparation method of a kind of double olefin copolymer, comprise the following steps: by rare earth catalyst, alkyl
Aluminum modification age resistor and diolefin mixing, be polymerized, obtain double olefin copolymer.The present invention is by age resistor modified for alkyl aluminum
Add diolefin polymerization when, participate in the polymerization of diolefin, make to be connected between little molecule age resistor and macromolecular chain, this
Sample is not only able to be prevented effectively from the problem such as the migration volatile, easy of little molecule age resistor and easy extraction, improves the antioxygen of rubber self
Change, aging-resistant performance；Being additionally, since between rubber and little molecule age resistor is to be connected by the way of chemical bond so that
Age resistor is easier to dispersion in macromolecular material matrix, further increases the antioxidation of rubber self, aging-resistant performance.
Further, described alkyl-modified age resistor is added diolefin polymerization when by the present invention, its anti-aging
Can be more excellent.
In order to further illustrate the present invention, a kind of double olefin copolymer of the present invention being provided below in conjunction with embodiment and
Preparation method is described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1～5
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 5mL-3The butadiene hexane solution of mol/mL, wherein the rubbing of butadiene and rare earth compound rare earth elements
That ratio is the 2 × 10 of 5:1,30mL-3The component E hexane solution of mol/mL, wherein alkyl aluminum compound is dilute with rare earth compound
The mol ratio of earth elements is 30:1, is aged 5 minutes at 80 DEG C, adds the 2 × 10 of 20mL-4The component C hexane solution of mol/mL, its
Middle component C is 2:1 with the mol ratio of rare earth compound rare earth elements, adds hexane solution, and being made into concentration is 2 × 10-5mol/
The rare earth catalyst of mL, is aged 5 minutes at 80 DEG C, obtains the rare earth catalyst for polymerized butadiene.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL butadiene hexane solution, then adds
Enter to prepare the rare earth catalyst of polybutadiene.The molal quantity of this catalyst agent Nd is 3 × 10 with the mol ratio of addition monomer-6mol/
G, reacts 24 hours under the conditions of 0 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes, is dried under vacuum to constant weight,
To polybutadiene.
The performance parameter of the polybutadiene that the embodiment of the present invention 1～5 obtains sees table 1, and table 1 is the embodiment of the present invention 1～5
The performance parameter of the polybutadiene obtained.
The performance parameter of the polybutadiene that table 1 embodiment of the present invention 1～5 obtains
Embodiment 6～9
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 10mL-3The isoprene hexane solution of mol/mL, wherein isoprene and rare earth compound Rare Earth Elements
Mol ratio is 10:1,15mL the 2 × 10 of element-3The component E hexane solution of mol/mL, wherein alkyl aluminum is dilute with rare earth compound
The mol ratio of earth elements is 15:1, and adding concentration is 2 × 10-3The component E hexane solution of mol/mL, is aged 15 minutes at 50 DEG C,
Add the 2 × 10 of 10mL-4The component C hexane solution of mol/mL, wherein component C and the mol ratio of rare earth compound rare earth elements
For 1:1, adding hexane solution, being made into concentration is 2 × 10-5The rare earth catalyst of mol/mL, is aged 30 minutes at 50 DEG C, is used
Rare earth catalyst in polymerized isoprene.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL isoprene hexane solution, then
The rare earth catalyst of polyisoprene is prepared in addition.The molal quantity of this catalyst agent Nd is 6 × 10 with the mol ratio of addition monomer- 6Mol/g, reacts 1 hour under the conditions of 50 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes, is dried under vacuum to perseverance
Weight, obtains polyisoprene.
The performance parameter of the polybutadiene that the embodiment of the present invention 6～9 obtains sees table 2, and table 2 is the embodiment of the present invention 6～9
The performance parameter of the polybutadiene obtained.
The performance parameter of the polybutadiene that table 2 embodiment of the present invention 6～9 obtains
Embodiment 10～13
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 10mL-3The butadiene hexane solution of mol/mL, wherein butadiene and rare earth compound rare earth elements
Mol ratio is the 2 × 10 of 10:1,20mL-3The alkyl aluminum hexane solution of mol/mL, wherein alkyl aluminum and rare earth compound middle rare earth
The mol ratio of element is 20:1, is aged 15 minutes at 50 DEG C, adds the 2 × 10 of 3mL-4The component C hexane solution of mol/mL, wherein
Component C is 3:1 with the mol ratio of rare earth compound rare earth elements, adds hexane solution, and being made into concentration is 2 × 10-5mol/mL
Rare earth catalyst, 60 DEG C be aged 30 minutes, obtain the rare earth catalyst for polymerized butadiene.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL butadiene hexane solution, adds E group
Point, the rare earth catalyst of polybutadiene is prepared in then addition.The molal quantity of this catalyst agent Nd is 1 with the mol ratio of addition monomer
×10-6Mol/g, reacts 6 hours under the conditions of 50 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes, and vacuum drying
To constant weight, obtain polybutadiene.The performance parameter of the polybutadiene that the embodiment of the present invention 10～13 obtains sees table 3, and table 3 is this
The performance parameter of the polybutadiene that inventive embodiments 10～13 obtains.
The performance parameter of the polybutadiene that table 3 embodiment of the present invention 10～13 obtains
Embodiment 14～16
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 20mL-3The isoprene hexane solution of mol/mL, wherein isoprene and rare earth compound Rare Earth Elements
Mol ratio is 20:1,25mL the 2 × 10 of element-3The alkyl aluminum hexane solution of mol/mL, wherein in alkyl aluminum and rare earth compound
The mol ratio of rare earth element is 25:1, adds hexane solution, is aged 60 minutes at 0 DEG C, and being made into concentration is 2 × 10-5Mol/mL's
Rare earth catalyst.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL isoprene hexane solution, adds
Component E, the rare earth catalyst of polyisoprene is prepared in then addition.The molal quantity of this catalyst agent Nd with add monomer mole
Ratio is 6 × 10-6Mol/g, reacts 5 hours under the conditions of 70 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes, very
Sky is dried to constant weight, obtains isoprene.The performance parameter of the polybutadiene that the embodiment of the present invention 14～16 obtains sees table 4,
Table 4 is the performance parameter of the polybutadiene that the embodiment of the present invention 14～16 obtains.
The performance parameter of the polybutadiene that table 4 embodiment of the present invention 14～16 obtains
The present invention is according to GB/T3512-2014 vulcanite or hot shortness's rubber hot-air accelerated ageing and heat resistant test side
Method, tests the diene that the embodiment of the present invention 5, embodiment 6, embodiment 10, embodiment 13, embodiment 15 and embodiment 16 obtain
The ageing resistace of hydrocarbon polymer, as shown in Table 1 and Table 2, Fig. 1 is that in the embodiment of the present invention and comparative example, polybutadiene is old to result
Changing time test curve, Fig. 2 is polyisoprene ageing time test curve in the embodiment of the present invention and comparative example.
Comparative example 1～2
Polybutadiene rubber (Lanxess Corporation rare earth polybutadiene rubber CB24) and polyisoprene rubber (Russia sieve is buied from market
This rare-earth isoprene rubber Russia-5), test its ageing resistace respectively.Result is shown in that Fig. 1 and Fig. 2, Fig. 1 are the embodiment of the present invention
With polybutadiene ageing time test curve in comparative example, Fig. 2 is that in the embodiment of the present invention and comparative example, polyisoprene is aging
Time test curve.
Comparative example 3
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 5mL-3The butadiene hexane solution of mol/mL, wherein the rubbing of butadiene and rare earth compound rare earth elements
That ratio is the 2 × 10 of 5:1,30mL-3The Al (i-Bu) of mol/mL2H hexane solution, wherein Al (i-Bu)2In H and rare earth compound
The mol ratio of rare earth element is 30:1, is aged 10 minutes at 50 DEG C, adds the 2 × 10 of 20mL-4The component C hexane of mol/mL is molten
Liquid, wherein component C is 2:1 with the mol ratio of rare earth compound rare earth elements, adds hexane solution, and being made into concentration is 2 × 10- 5The rare earth catalyst of mol/mL, is aged 60 minutes at 50 DEG C, obtains the rare earth catalyst for polymerized butadiene.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL butadiene hexane solution, then adds
Enter to prepare the rare earth catalyst of polybutadiene.The molal quantity of this catalyst system Nd is 3 × 10 with the mol ratio of addition monomer- 6Mol/g, reacts 24 hours under the conditions of 0 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes, is dried under vacuum to perseverance
Weight, obtains polybutadiene, and cis-Isosorbide-5-Nitrae structure (%) is 97.8, and Mooney viscosity is 46.7.
Comparative example 4
Under nitrogen protection, in dry hydrogen-catalyst reactor, it is sequentially added into the 2 × 10 of 10mL-4The rare earth of mol/mL
Compound, the 2 × 10 of 20mL-3The isoprene hexane solution of mol/mL, wherein isoprene and rare earth compound Rare Earth Elements
Mol ratio is 20:1,25mL the 2 × 10 of element-3The Al (i-Bu) of mol/mL3Hexane solution, wherein Al (i-Bu)3With rare earth
The mol ratio of compound rare earth elements is 25:1, adds hexane solution, is aged 30 minutes at 50 DEG C, and being made into concentration is 2 × 10- 5The rare earth catalyst of mol/mL.
Under nitrogen protection, adding 1L monomer concentration in polymeric kettle is 20g/100mL isoprene hexane solution, adds
Component E, the rare earth catalyst of polyisoprene is prepared in then addition.The molal quantity of this catalyst system Nd rubs with addition monomer
Your ratio is 6 × 10-6Mol/g, reacts 5 hours under the conditions of 70 DEG C, and settle out in ethanol polymer, after washing with alcohol extrudes,
It is dried under vacuum to constant weight, obtains isoprene.Cis-Isosorbide-5-Nitrae structure (%) is 97.0, and Mooney viscosity is 79.6.
In Fig. 1,1 is the ageing time test curve of polybutadiene in comparative example 3 of the present invention；2 is that the embodiment of the present invention 5 obtains
The ageing time test curve of the polybutadiene arrived；3 is the ageing time test song of polybutadiene rubber in comparative example 1 of the present invention
Line；4 is the ageing time test curve of polybutadiene in the embodiment of the present invention 10；The 5 poly-fourths obtained for the embodiment of the present invention 13
The test curve of the ageing time of diene.In Fig. 2,1 is polyisoprene ageing time test curve in comparative example 4 of the present invention；2
For polyisoprene ageing time test curve in the embodiment of the present invention 6；3 is that in the embodiment of the present invention 15, polyisoprene is aging
Time test curve；4 is the ageing time test curve of polyisoprene rubber in comparative example 2 of the present invention；5 implement for the present invention
The ageing time test curve of polyisoprene in example 16.
By Fig. 1 and Fig. 2 it can be seen that the physical doping little molecule age resistor commercially available with comparative example 1 and comparative example 2 double
Olefin polymer carries out ageing time contrast, and the age resistor that in polymerization process, addition alkyl aluminum is modified is along with the increase of consumption, always
Changing effect to be remarkably reinforced, as E: during monomer=2 ‰ (w/w), anti-aging effect is significantly better than commercially available prod.Preparing rare earth catalyst
The age resistor that the alkyl aluminum added during agent is modified, because being to add according to the proportioning of alkyl aluminum, is likely to be due to addition phase
To relatively low, anti-aging effect is less than industrial products, but compared with the sample being not added with age resistor, has still functioned as age inhibiting work
With.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a preparation method for double olefin copolymer, comprises the following steps:
Rare earth catalyst, alkyl aluminum modification age resistor and diolefin are mixed, is polymerized, obtains double olefin copolymer.
Preparation method the most according to claim 1, it is characterised in that described rare earth catalyst by include rare earth compound,
First diolefin, alkyl aluminum compound and muriatic mixture are made；
The preparation process of described double olefin copolymer specifically includes:
A1) rare earth compound, the first diolefin, alkyl aluminum compound and chloride are mixed, be aged, obtain rare earth catalyst
Agent；
B1) described rare earth catalyst, alkyl aluminum modification age resistor and the second diolefin are mixed, be polymerized, obtain diolefin
Polymer；
Described first diolefin and the second diolefin are independently selected from butadiene or isoprene.
Preparation method the most according to claim 1, it is characterised in that described rare earth catalyst by include rare earth compound,
First diolefin and muriatic mixture are made；
The preparation process of described double olefin copolymer specifically includes:
A2) rare earth compound, the first diolefin, alkyl aluminum modification age resistor and chloride are mixed, be aged, obtain rare earth
Catalyst；
B2) described rare earth catalyst and the second diolefin are mixed, be polymerized, obtain double olefin copolymer；
Described first diolefin and the second diolefin are independently selected from butadiene or isoprene.
4. according to the preparation method described in claims 1 to 3 any one, it is characterised in that described alkyl aluminum modification age resistor
Prepare according to following steps:
Alkyl aluminum compound and age resistor are mixed, reacts, obtain the age resistor that alkyl aluminum is modified.
Preparation method the most according to claim 4, it is characterised in that when preparing alkyl aluminum modification age resistor, described alkyl
Aluminium compound includes trialkylaluminium and/or alkyl-al hydride；
Described age resistor include phenol antiager, virtue amines antioxidants, containing the one in Phosphorus age resistor and sulfur-bearing class age resistor
Or it is several；
The mol ratio of described alkyl aluminum compound and age resistor is (1～10): 1.
6. according to the preparation method described in claims 1 to 3 any one, it is characterised in that described rare earth compound includes dilute
In soil carboxylate, rare earth superphosphate, rare earth acidity phosphonate, alkoxy rare-earth and rare earth chloride electron donor coordination compound
One or more；
Rare earth element in described rare earth compound includes one or more in neodymium, lanthanum and shirt.
7. according to the preparation method described in claims 1 to 3 any one, it is characterised in that described chloride includes a chlorine two
Aluminium isobutyl, aluminium diethyl monochloride, sesquialter aluminium ethide, tertiary butyl chloride, benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyl
One or more in dichlorosilane, trim,ethylchlorosilane and Silicon chloride..
Preparation method the most according to claim 2, it is characterised in that described step A1) in rare earth compound, alkyl aluminum
The mol ratio of compound, chloride and the first diolefin is 1:(5～30): (1～3): (5～20)；
Described step B1) in the molal quantity of rare earth catalyst rare earth elements and the mass ratio of the second diolefin be (1 × 10-6～6 × 10-6) mol:1g；
Described step B1) in alkyl aluminum modification age resistor and the mass ratio of the second diolefin be (0.5～2): 1000.
Preparation method the most according to claim 3, it is characterised in that described step A2) in rare earth compound, alkyl aluminum
The mol ratio of modified age resistor, chloride and the first diolefin is 1:(5～40): (1～3): (5～20)；
Described step B2) in the molal quantity of rare earth catalyst rare earth elements and the mass ratio of the second diolefin be (1 × 10-6～6 × 10-6) mol:1g.
10. a double olefin copolymer, is prepared by the preparation method described in claim 1～9 any one.
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| CN113968935A (en) * | 2021-11-11 | 2022-01-25 | 中国科学院长春应用化学研究所 | Phospholipid compound modified butadiene-isoprene copolymer rubber, preparation method thereof and vulcanized rubber |
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