CN105860407A - Olefin polymer, preparation method and application thereof - Google Patents
Olefin polymer, preparation method and application thereof Download PDFInfo
- Publication number
- CN105860407A CN105860407A CN201510026493.0A CN201510026493A CN105860407A CN 105860407 A CN105860407 A CN 105860407A CN 201510026493 A CN201510026493 A CN 201510026493A CN 105860407 A CN105860407 A CN 105860407A
- Authority
- CN
- China
- Prior art keywords
- olefin polymer
- weight
- conjugated diene
- content
- monovinylarene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an olefin polymer, a preparation method and an application thereof. The olefin polymer contains a star-shaped conjugated diene homopolymer, a liner conjugated diene homopolymer and a liner conjugated diene-mono-vinyl aromatic copolymer, the molecular weight distribution of the olefin polymer is trimodal distribution, the mooney viscosity ML1+4 of the olefin polymer at the temperature of lower than 100 DEG C is 50-70, and the viscosity of a styrene solution with concentration being 5wt% of the olefin polymer is 0.02-0.04 Pa.s at the temperature of 25 DEG C. The olefin polymer can endow resin with high impact intensity and high glossiness.
Description
Technical field
The present invention relates to a kind of olefin polymer, the preparation method of a kind of olefin polymer, by the party's legal system
The standby olefin polymer obtained and described olefin polymer are as polystyrene resin and/or acrylic nitrile-butadiene
The application of the modifying agent of styrene resin.
Background technology
For improving the resistance to of polystyrene (PS) resin and acrylonitrile-butadiene-styrene (ABS) (ABS) resin
Impact, prior art is generally introduced therein to modification rubber.The biggest rubber size can
Make resin have higher impact strength, but the glossiness of resin can be reduced, although less rubber size
Ensure that the high gloss of resin, but easily imbed in stress crack, cause resin impact resistance to decline.
Accordingly, it would be desirable to control in certain size by rubber size, reach to improve the glossiness of resin, again
The purpose of the impact resistance of resin can be kept.In general, controlling rubber particle size can be by controlling
(when 25 DEG C, the styrene solution of modified rubber containing 5 weight % is viscous for the SV value of resin modified rubber
Degree) mode realize.
Additionally, introduce the equal poly structure of monovinylarene in modified rubber strand, not only can improve and change
Property rubber intermiscibility in resin, also can improve the index of refraction of modified rubber simultaneously, make modified rubber
Index of refraction is close with the index of refraction of resin matrix, and then eliminates the light scattering within resin, the light of resin
Pool degree is improved, and the transparency of resin is also improved simultaneously.
In order to improve the resistance to impact of acrylonitrile-butadiene-styrene (ABS) (ABS) resin, and keep surface
Glossiness is basically unchanged, and US4524180 discloses a kind of monovinylarene compositions, is wherein dispersed with
Dience rubber (polybutadiene) and butadiene are unsaturated with mono vinyl arenes monomer and/or ethylenic
The mixture of lonitrile copolymer.US4587294 discloses a kind of continuous preparation and has the rubber of high-impact performance
Preparation method, the method include by the mixture of aromatic hydrocarbon monomer, acrylonitrile monemer and polybutadiene with
Initiator introduces in the first reactor, and carries out polyreaction under high shear is stirred, so that rubber components
Inversion of phases is discrete particles, and then the first product introduces the second reactor and more reactor
In react further.
US4639494 discloses the preparation method of a kind of resin with high-impact performance, the method include by
Styrene carries out Raolical polymerizable in the presence of butadiene rubber, and described butadiene rubber is for passing through
1,3-butadiene homopolymerization or by 1,3-butadiene and the styrene copolymerized highly-branched polymers obtained,
Then being reacted with polyfunctionality halogen contained compound further by the polymer obtained, wherein branched structure contains
Amount is more than or equal to 60%, and 1,2 structure accounts for 18-32 weight % of polybutadiene segments, containing of styrene block
Amount is 8-10 weight %, and Mooney viscosity of rubber is 40-90, and SV value is 0.06-0.09Pa s.This rubber
Although there is high impact strength for modified resin, but the SV value of rubber being the highest, so can lead
Cause the decline of modified resinous luster degree.
US4421895 discloses and uses the SV value line equal to or less than 0.08Pa s in the preparation of ABS
Type Styrene-Butadiene block dience rubber, it is thus achieved that have and be dispersed in substrate less than 0.7 μ m in size
In rubber grain, and therefore obtain there is high performance attractive in appearance, the ABS of high glaze.But, but damage
The physical mechanical feature of ABS resin, particularly resistance to impact are done harm to.
In prior art, Star-shaped Low-cis-Polybutadiene rubber and line style butylbenzene block rubber many employings lithiums system
Anionic solution polymerization technology synthesize, the polymerization glue obtained must through agglomeration process remove solvent therein,
After be dried through two-shipper, vulcanization bed forced air drying, briquetting, be packaged into finished product.In view of above-described
Aftertreatment technology and the performance of rubber product, the Mooney viscosity (ML of polymerization glue1+4, 100 DEG C) and it is raw
Producing the leading indicator controlled, if product Mooney viscosity is too high, sizing material easy efflorescence during cohesion, before causing two-shipper
Leaking glue at glue grain sieves serious, the difficulty of two-shipper material feeding simultaneously, product is difficult to by compound stalk forming；If producing
Product Mooney viscosity is the lowest, then when condensing, bad dispersibility between sizing material, easily assembles in bulk, on the one hand easily makes
Become condensing field, the blocking of process pipelines between discharging pump and discharging pump to two-shipper, on the other hand, easily cause
In two-shipper, roller embraced by sizing material, not only affects drying effect, is also easily generated plasticizing glue, causes product gel content
Higher, affect resin property.
In prior art, when preparing SV value resin modified rubber between 0.02-0.40Pa s,
For design molecular weight be 50,000-60,000, the Star-shaped Low-cis-Polybutadiene of coupling efficiency 70-80%
For rubber, between its Mooney viscosity is generally between 30-40, Mooney viscosity is on the low side, cohesion and post processing
Difficulty.And for design molecular weight be 10,000-15,000, styrene-content be about 20-40 weight %
Line style butylbenzene block rubber for, its Mooney viscosity is typically in the range of between 110-150, this Mooney viscosity
Under, during cohesion, rubber efflorescence is serious, post processing difficulty.
In sum, it is badly in need of exploitation a kind of to ensure the impact strength of modified resin, can improve again
Resinous luster degree polymer-modified.
Summary of the invention
The invention aims to overcome the existing modification rubber of employing to polystyrene resin and/or
When acrylonitrile-butadiene-styrene resin is modified processing, single variety modified rubber can not be expired simultaneously
The defect that foot resin impact strength and resinous luster degree require, and provide a kind of and new can give tree simultaneously
Impact strength that fat is high and the olefin polymer of high glossiness, the preparation method of described olefin polymer,
The olefin polymer that prepared by the method and described olefin polymer as polystyrene resin and/
Or the application of the modifying agent of acrylonitrile-butadiene-styrene resin.
The present invention provides a kind of olefin polymer, and wherein, described olefin polymer contains star-like conjugation two
Olefin homo, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymer,
The molecular weight distribution of described olefin polymer is tri-modal distribution, described olefin polymer door at 100 DEG C
Buddhist nun's viscosity ML1+4For 50-70, and the styrene solution of the described olefin polymer that concentration is 5 weight %
Viscosity at 25 DEG C is 0.02-0.04Pa s.
Present invention also offers the preparation method of a kind of olefin polymer, the method includes:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
The first polyreaction is carried out in atent solvent；
(2) when conversion ratio >=97% of described conjugated diene monomer, by the first polymeric reaction product
Coupling reaction is carried out with polyfunctionality coupling agent；Total coupling group in described polyfunctionality coupling agent and institute
The mol ratio stating single functionality organic lithium initiator is 0.40-0.55:1；
(3) in the presence of terminator, the product that step (2) obtains is entered with mono vinyl arenes monomer
Row the second polyreaction so that the conversion ratio of described mono vinyl arenes monomer is >=97%；Described termination
Agent is 0.1-0.15:1 with the mol ratio of described single functionality organic lithium initiator.
Present invention also offers the olefin polymer prepared by said method.
Additionally, present invention also offers described olefin polymer as polystyrene resin and/or acrylonitrile-
The application of the modifying agent of butadiene styrene resin.
The present inventor finds after further investigation, in non-polar solven, uses stable list
Degree of functionality organic lithium initiator causes conjugate diene monomer polymerization, through polyfunctionality coupling agent moiety
After, add terminator and mono vinyl arenes monomer is polymerized further, can prepare and have simultaneously
Star-like conjugated diene homopolymers, linear conjugated diene homopolymers and linear conjugated alkadienes-mono-vinyl
The olefin polymer of arene copolymer, the molecular weight distribution of this olefin polymer is tri-modal distribution, this polymerization
Thing has suitable Mooney viscosity (the Mooney viscosity ML at 100 DEG C1+4For 50-70) and suitable SV
Value (0.02-0.04Pa s), and when resin is modified by this olefin polymer, in the power ensureing resin
On the premise of learning performance, the glossiness of resin can be effectively improved.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The olefin polymer that the present invention provides contains star-like conjugated diolefin homopolymerization thing, linear conjugated alkadienes
Homopolymer and linear conjugated diene-monovinylarene copolymer, the molecular weight of described olefin polymer divides
Cloth is tri-modal distribution, described olefin polymer Mooney viscosity ML at 100 DEG C1+4For 50-70 and dense
Degree is that the styrene solution of the described olefin polymer of 5 weight % viscosity at 25 DEG C is
0.02-0.04Pa·s。
The present invention is equal to conjugated diolefin homopolymerization thing star-like in described olefin polymer, linear conjugated alkadienes
The content of polymers and linear conjugated diene-monovinylarene copolymer is not particularly limited, such as,
On the basis of the gross weight of described olefin polymer, the content of described star-like conjugated diolefin homopolymerization thing is permissible
For 40-55 weight %, the content of described linear conjugated diene homopolymers can be 10-15 weight %,
The content of described linear conjugated diene-monovinylarene copolymer can be 35-45 weight %.
According to the present invention, in order to preferably improve when enabling described olefin polymer as modifier
The glossiness of resin, it is preferable that on the basis of the gross weight of described olefin polymer, described linear conjugated
In diene-monovinylarene copolymer, the content of monovinylarene homopolymerization section is 20-40 weight %, more
It is preferably 25-35 weight %.In the present invention, described monovinylarene homopolymerization section refers to described line style
Continuously containing six and more than six mono-vinyls on conjugated diene-monovinylarene copolymer strand
Aromatic hydrocarbons construction unit.Additionally, mono-vinyl in described linear conjugated diene-monovinylarene copolymer
The content of the micro-block of aromatic hydrocarbons is theoretically the lowest more good, but from the ready availability angle of raw material, preferably
Ground, on the basis of the gross weight of described olefin polymer, described linear conjugated diene-monovinylarene
In copolymer, the content of the micro-block of monovinylarene is 0-3 weight %, more preferably 0-2 weight %.
In the present invention, the micro-block of described monovinylarene refers to described linear conjugated diene-mono-vinyl virtue
Continuously containing five and less than five monovinylarene construction units on hydrocarbon copolymer strand.
According to the present invention, in described olefin polymer, conjugated diene construction unit can be with 1, and 2-ties
Presented in structure, it is also possible to Isosorbide-5-Nitrae-structure (including cis-Isosorbide-5-Nitrae-structure and anti-form-1,4-structure)
Form exists.The present invention is to 1,2-construction unit, cis-1,4-knot in described conjugated diene construction unit
Structure unit and anti-form-1, the content of 4-construction unit is all not particularly limited, such as, with described alkene
In polymer on the basis of the content of conjugated diene construction unit, in described conjugated diene construction unit 1,2-
The content of construction unit can be 5-15 weight %, and the content of cis-Isosorbide-5-Nitrae-construction unit can be 25-40
Weight %, anti-form-1, the content of 4-construction unit can be 45-65 weight %；Preferably, with described alkene
In hydrocarbon polymer on the basis of the content of conjugated diene construction unit, in described conjugated diene construction unit
The content of 1,2-construction unit can be 8-12 weight %, and the content of cis-Isosorbide-5-Nitrae-construction unit can be
30-35 weight %, anti-form-1, the content of 4-construction unit can be 55-60 weight %.
According to the present invention, described conjugated diene construction unit is the structure list derived from conjugated diene
Unit, the construction unit i.e. formed by conjugate diene polymerization.Described conjugated diene refers in molecular structure
Various unsaturated acyclic hydrocarbons containing conjugated double bond (that is ,-C=C-C=C-).The kind of described conjugated diene
Class can be the conventional selection of this area, is not particularly limited, and such as, described conjugated diene is permissible
Selected from C4-C12Straight or branched conjugated diene, preferably C4-C8Straight or branched conjugated diene, more excellent
Elect the one in butadiene, isoprene and pentadiene as.
According to the present invention, described monovinylarene construction unit is the structure derived from monovinylarene
Unit, is i.e. polymerized the construction unit formed by monovinylarene.The kind of described monovinylarene can
Thinking the conventional selection of this area, be not particularly limited, such as, described monovinylarene can select
From C8-C20Monovinylarene, preferably C8-C12Monovinylarene, more preferably styrene, right
One in methyl styrene and α-methyl styrene.
Molecular size range and the peak area size at three peaks of described olefin polymer are not all had by the present invention
Limit especially, such as, the peak molecular weight (Mp) at three peaks in the distribution of described weight of otefi pi polymer
150,000-190,000,100,000-150,000 He can be respectively according to retention time is ascending,
50,000-60,000, the peak area percent at three peaks can be respectively according to retention time is ascending
40-55%, 35-45% and 10-15%；Preferably, three peaks in the distribution of described weight of otefi pi polymer
Peak molecular weight according to retention time ascending be respectively 125,000-155,000,
115,000-145,000 and 45,000-55, the peak area percent at 000, three peaks according to retention time by little
It is respectively 42-53%, 36-40% and 11-14% to big.Additionally, the distribution of described weight of otefi pi polymer
In the molecular weight distributing index at three peaks be both preferably 1.05-1.2.
The preparation method of the olefin polymer that the present invention provides comprises the following steps:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
The first polyreaction is carried out in atent solvent；
(2) when conversion ratio >=97% of described conjugated diene monomer, by the first polymeric reaction product
Coupling reaction is carried out with polyfunctionality coupling agent；Total coupling group in described polyfunctionality coupling agent and institute
The mol ratio stating single functionality organic lithium initiator is 0.40-0.55:1；
(3) in the presence of terminator, the product that step (2) obtains is entered with mono vinyl arenes monomer
Row the second polyreaction so that the conversion ratio of described mono vinyl arenes monomer is >=97%；Described termination
Agent is 0.1-0.15:1 with the mol ratio of described single functionality organic lithium initiator.
The method that preparation method is batchwise polymerization of the above-described olefin polymer of the present invention, described interval
Polymerization refers to carry out successively above-mentioned first polyreaction, coupling reaction and the in same polymerization reaction kettle
Dimerization is reacted.According to a kind of detailed description of the invention of the present invention, the preparation method of described olefin polymer
May include that and solvent, conjugated diene monomer, initiator and other reaction promoter are added polyreaction
In still, after reaction a period of time, in polymerization reaction kettle, add coupling agent, after certain time of staying,
In polymerization reaction kettle, add terminator and single vinylaromatic monomer, discharge after certain time of staying.
According to the present invention, the kind of described noble gas can be the conventional selection of this area, such as, institute
State noble gas and can include but not limited at least one in nitrogen, argon and helium.
The kind of described atent solvent can be the conventional selection of this area, for example, it is possible to for having 5-12
The hydro carbons of individual carbon atom and their cyclic analogs, preferably propane, butane, pentane, hexane,
Heptane, octane, decane, Pentamethylene., methyl cyclopentane, hexamethylene, cycloheptane, raffinate oil, just oneself
At least one in alkane and cyclooctane, more preferably raffinates oil, at least one in normal hexane and hexamethylene.
According to the present invention, described single functionality organic lithium initiator can be conventional in anionic polymerisation field
Single functionality organo-lithium compound in trigger monomer polymerization, it is preferable that described single functionality organolithium draws
Sending out agent can be for the compound as shown in formula (I):
RLi (I)
Wherein, R is the alkyl of straight or branched, cycloalkyl or aryl, preferably ethyl, propyl group, different
Propyl group, normal-butyl, sec-butyl, amyl group, hexyl, cyclohexyl, phenyl, aminomethyl phenyl or naphthyl, more
It is preferably normal-butyl or sec-butyl.
There is no particular limitation to the consumption of described single functionality organic lithium initiator for the present invention, can basis
The molecular size range needing the first polymerization reaction monomer obtained selects.Usually, obtain when needs
During bigger the first polymerization reaction monomer of molecular weight, then can reduce the use of single functionality organic lithium initiator
Amount；And when needing the first polymerization reaction monomer obtaining molecular weight, then can increase single functionality
The consumption of organic lithium initiator.As a rule, relative to the conjugated diene monomer of 100g, described list
The consumption of degree of functionality organic lithium initiator can be 1.66-2.00mmol.
According to the present invention, described polyfunctionality coupling agent can be selected from polyfunctionality commonly used in the art
Coupling agent, as long as making in olefin polymer containing star-like conjugated diolefin homopolymerization thing.Such as, institute
Stating polyfunctionality coupling agent can be polyfunctionality halogenide, preferably methyl trifluoro SiClx, methyl trichlorine
SiClx, methyl tribromo SiClx, methyl triiodo SiClx, methyl trifluoro stannum, tin methyltrichloride, methyl
Tribromide stannum, methyl triiodide stannum, butyl trifluoro SiClx, butyl trichlorosilicane, butyl tribromo SiClx,
Butyl triiodo SiClx, Silicon fluoride., Silicon chloride., Silicon bromide., silicon tetraiodide, tin tetrafluoride, four
At least one in stannic chloride, tin tetrabromide, tin tetraiodide, butter of tin, butter of tin, more preferably
For Silicon chloride. and/or butter of tin, most preferably Silicon chloride..
According to the present invention, carry out coupling reaction to control only part the first polymeric reaction product, and remain
First polymeric reaction product of part still is able to carry out follow-up termination reaction or the second polyreaction, thus
Make the olefin polymer obtained contains simultaneously star-like conjugated diolefin homopolymerization thing, linear conjugated alkadienes equal
Polymers and linear conjugated diene-monovinylarene copolymer, the total idol in described polyfunctionality coupling agent
Symbasis group can be 0.40-0.55:1 with the mol ratio of described single functionality organic lithium initiator, is preferably
0.45-0.54:1.In the present invention, the total coupling group in described polyfunctionality coupling agent refers to many officials
The total content of coupling group in energy degree coupling agent.
According to the present invention, the kind of described terminator can be selected from terminator commonly used in the art, example
As, can be at least one in water and/or alcohols, preferably water, methanol, ethanol, isopropanol, more
It is preferably water.Additionally, so that described coupling reaction product does not occurs a polymer part for coupling
Carry out terminating reaction, and another part carries out the second polyreaction, described terminator and described single functionality
The mol ratio of organic lithium initiator can be 0.1-0.15:1, preferably 0.11-0.14:1.
The consumption of described conjugated diene monomer and mono vinyl arenes monomer is not had the most especially by the present invention
Limit, such as, relative to the conjugated diene monomer of 100 weight portions, described mono vinyl arenes monomer
Consumption be 20-40 weight portion, more preferably 25-35 weight portion.Additionally, described conjugated diene list
The kind of body and mono vinyl arenes monomer has been described above being described, then this does not repeats.
According to the present invention, the method is additionally included in step 1) in add structure regulator and/or gel suppression
Agent.The kind of described structure regulator can be the conventional selection of this area, for example, it is possible to selected from nitrogenous,
At least one in oxygen-containing, sulfur-bearing, phosphorous polar compound, preferably ether, butyl oxide, dioxy
Six rings, oxolane, glycol dimethyl ether, two dry diethylene glycol dimethyl ethers, diphenyl ether, triethylamine, tetramethyl
In ethylenediamine, HMPA, potassium tert-butoxide, sodium alkyl benzene sulfonate and ethyl tetrahydrofurfuryl ether
At least one, more preferably oxolane and/or ethyl tetrahydrofurfuryl ether.Further, when using tetrahydrochysene
When furan is as structure regulator, the consumption of described oxolane can be polymerization system concentration
80-150ppm；When using ethyl tetrahydrofurfuryl ether as structure regulator, described ethyl tetrahydrofurfuryl
Ether can be the 3-9ppm of polymerization system concentration.
The kind of described gel inhibitor can be the conventional selection of this area, for example, it is possible to selected from 1,2-
Butadiene, tertiary amoxy potassium (KTA)/Silicon chloride. (SiCl4), tetramethylethylenediamine (TMEDA)/1,2-fourth
At least one in diene and THF/1,2-butadiene.Additionally, the consumption of described gel inhibitor can be
The 60-150ppm of polymerization system concentration, preferably 80-120ppm.
The condition of described first polyreaction is not particularly limited by the present invention, as long as enabling to described
Conjugated diene monomer carries out being polymerized and make the conversion ratio of monomer to reach >=97%, such as, described
The condition of one polyreaction includes: polymerization temperature can be 40-130 DEG C, preferably 70-110 DEG C；Polymerization
Pressure can be 0.1-1.5MPa, preferably 0.2-0.5MPa；Polymerization time can be 10-70 minute,
It is preferably 30-60 minute.
The condition of coupling reaction described in step (2) is also not particularly limited by the present invention, if energy
Enough make described first polymeric reaction product of part and described coupling agent generation coupling reaction, such as,
The condition of described coupling reaction includes: coupling temperature can be 40-130 DEG C, preferably 70-110 DEG C；Even
Connection pressure can be 0.1-1.5MPa, preferably 0.2-0.5MPa；；Coupling time can be 20-70 minute,
It is preferably 30-60 minute.
The condition of described second polyreaction is also not particularly limited by the present invention, as long as enabling to step
Suddenly in the coupling reaction product that (2) obtain, the part in non-coupling polymer is reacted with terminator, and
And another part continues carry out polyreaction with mono vinyl arenes monomer and make mono vinyl arenes monomer
Conversion ratio reaches >=97%, and such as, the condition of described second polyreaction includes: polymerization temperature can
Think 40-130 DEG C, preferably 70-110 DEG C；Polymerization pressure can be 0.1-1.5MPa, is preferably
0.2-0.5MPa；Polymerization time can be 20-70 minute, preferably 30-60 minute.
In the present invention, described pressure refers both to gauge pressure.
Additionally, for the ageing-resistant performance improving described olefin polymer, generally to complete the second polymerization anti-
After should, in addition it is also necessary to described second polymeric reaction product is contacted with age resistor.Described age resistor can be
The existing various material being prevented from ageing of rubber, for example, it is possible to be that phenol antiager and/or amine are prevented
Old agent, specifically can be selected from 2,6 ditertiary butyl p cresol (being called for short Irganox 264), tert-butyl o benzene
Diphenol, 2,2 '-methylene-bis-(4-methyl-6-tert-butylphenols) (be called for short Irganox 2246) and 2,4-bis-is (just
Octyl group sulfur methylene) one or more in-6-methylphenol (be called for short Irganox 1520).With whole poly-
On the basis of the total monomer weight added during conjunction, the consumption of described age resistor typically 0.1-2 weight
Amount %.
After polyreaction completes, need the solvent removal in the olefin polymer that will finally give.De-
Except the method for solvent is known to the skilled person, for example, it is possible to by alcoholization precipitation, centrifugation,
The modes such as filtration, decant, steam cohesion are by olefin polymer Precipitation from solvent, it is also possible to adopt
By stripping mode, the volatile solvent in olefin polymer is separated off.Equal to these those skilled in the art
Can know, will not be described in great detail at this.
Present invention also offers the olefin polymer prepared by said method.
Additionally, present invention also offers described diene polymer as polystyrene resin and/or propylene
The application of the modifying agent of nitrile-butadiene styrene resin.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example:
1, in polymerization process, conjugated diene monomer, the conversion ratio of mono vinyl arenes monomer use
Shimadzu GC-14A flame gas chromatograph measures, and internal standard method calculates, and concrete calculating process is as follows:
St%=1-[(s/h)/(S/H)] × 100
Bd%=1-[(b/h)/(B/H)] × 100
Wherein, cinnamic peak area during s is the polymeric kettle outlet sample that GC measures；
B is the peak area of butadiene in the polymeric kettle outlet sample that GC measures；
H is the peak area sum of solvent in the polymeric kettle outlet sample that GC measures；
The unit inlet amount of styrene monomer, units/kg/h when S is polymerization；
The unit inlet amount of divinylic monomer, units/kg/h when B is polymerization；
H is the unit inlet amount of the solvent entering paradigmatic system, units/kg/h.
2, the SV value of polymer refers to the styrene solution of described olefin polymer that concentration is 5 weight %
Viscosity at 25 DEG C, it uses Cannon-Fenske type viscometer to test.
3, polymer Mooney viscosity utilize Japan Shimudzu ML tester (preheat 1 minute,
Rotate 4 minutes at 100 DEG C, value) test.
4, the mensuration of gel content (Gel%): polymer samples is done in 50 DEG C in vacuum drying oven
Dry to constant weight, weigh, be designated as W1, then dissolve dried copolymer with styrene (cinnamic
Consumption makes the concentration of polymer be 5 weight %), fully dissolve 135 DEG C of vibrations, then use 300
Mesh stainless (steel) wire filtered polymeric solution, by polymer undissolved on stainless (steel) wire in vacuum drying oven
It is dried 4 hours in 100 DEG C, weighs, be designated as W2, calculating gel content value, gel content value calculates
Formula is as follows: gel content value (weight %)=(W2/W1) × 100 (weight %).
5, concentration is the mensuration of styrene solution colourity of described olefin polymer of 5 weight %: use
GB/T 9282.1-2008 standard, with platinum-cobalt titer as reference colour, measures concentration by optical colorimetry.
6,1,2-structure (vinyl structure), cis-1,4-structure, anti-form-1,4-in polymer monomer unit
Structural content uses Switzerland's Bruker AVANCE-400 type nuclear magnetic resonance chemical analyser test, and room temperature measures,
Liquid pool method, solvent is CS2.
7, polymer molecular weight and molecular weight distribution use Japan's Shimadzu LC-10A series gel infiltration color
Spectrometer GPC tests.
Embodiment 1
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes a polymerization reaction kettle.At high pure nitrogen protective atmosphere
Under, in 5 liters of polymeric kettles, add raffinate oil 2730g, 1,3-butadiene 559g, 1，2-butadiene successively
0.395g, oxolane 0.329g, open stirring, adds n-butyl lithium initiator at a temperature of 50 DEG C
0.716g, carries out the first polyreaction, and reaction pressure is 0.1-0.3MPa, and reaction mass starts to warm up,
Arrive maximum temperature 90 DEG C when reacting 8 minutes, record divinylic monomer conversion ratio and reach 97%；Again
Silicon chloride. (total coupling group of Silicon chloride. and the mol ratio of n-BuLi is added in polymerization reaction kettle
For 0.55:1) coupling agent 0.261g, and temperature is controlled 70 DEG C, Stress control idol at 0.2 mpa
Connection reaction 30 minutes；After coupling reaction terminates, add (terminator water and n-BuLi in 0.020g water
Mol ratio be 0.1:1) styrene 373g, and temperature is controlled 70 DEG C, Stress control is at 0.2MPa
Under carry out the second polyreaction, polyase 13 records styrene monomer conversion rate and reaches 97% after 0 minute；Then
Add terminator isopropanol 0.235g and terminate reaction, and add the age resistor Irganox of monomer weight 0.2%
1520, then glue is carried out devaporation desolventizing process, obtains olefin polymer J1, this alkene gathers
The molecular weight distribution of compound J1 is tri-modal distribution, and its concrete analysis test result is as shown in table 1.
Embodiment 2
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes a polymerization reaction kettle.At high pure nitrogen protective atmosphere
Under, in 5 liters of polymeric kettles, add hexamethylene 2730g, 1,3-butadiene 444g, 1，2-butadiene successively
0.381g, oxolane 0.317g, add n-butyl lithium initiator 0.517g at a temperature of 53 DEG C and carry out the
One polyreaction, reaction pressure is 0.1-0.3MPa, and reaction mass starts to warm up, when reacting 10 minutes
Arrive maximum temperature 85 DEG C, record divinylic monomer conversion ratio and reach 97%；Add in polymeric kettle again
Enter Silicon chloride. (total coupling group of Silicon chloride. and the mol ratio of n-BuLi are 0.45:1) coupling agent
0.154g, and temperature is controlled 80 DEG C, Stress control at 0.3MPa under coupling reaction 40 minutes；Even
After connection reaction terminates, add containing 0.019g water (terminator water is 0.13:1 with the mol ratio of n-BuLi)
Styrene 190g, and temperature is controlled 80 DEG C, Stress control at 0.3MPa under carry out the second polymerization
Reaction, records styrene monomer conversion rate after being polymerized 40 minutes and reaches 97%；It is subsequently adding terminator isopropyl
Alcohol 0.204g terminates reacting, and adds the age resistor Irganox 1520 of monomer weight 0.2%, then to glue
Liquid carries out devaporation desolventizing process, obtains olefin polymer J2, the molecule of this olefin polymer J2
Amount is distributed as tri-modal distribution, and its concrete analysis test result is as shown in table 1.
Embodiment 3
Olefin polymer that this embodiment provides for the present invention is described and preparation method thereof.
Reaction unit used by this embodiment includes a polymerization reaction kettle.Under high pure nitrogen is protected, depend on
Secondary addition hexamethylene/normal hexane mixed solvent (weight ratio is 82/18) 2730g, 1,3-in 5 liters of polymeric kettles
Butadiene 337g, 1，2-butadiene 0.368g, ethyl tetrahydrofurfuryl ether 0.028g, at a temperature of 55 DEG C,
Adding n-BuLi 0.360g and carry out the first polyreaction, reaction pressure is 0.1-0.3MPa；Reaction mass
Starting to warm up, arrive maximum temperature 80 DEG C when reacting 12 minutes, high temperature recorded monomer after 10 minutes
Conversion ratio reaches 100%, then add in polymeric kettle Silicon chloride. (total coupling group of Silicon chloride. with just
The mol ratio of butyl lithium is 0.50:1) coupling agent 0.119g, and temperature is controlled at 75 DEG C, Stress control
Coupling reaction 35 minutes under 0.25MPa；After coupling reaction terminates, add containing 0.051g isopropanol (eventually
Only agent isopropanol is 0.15:1 with the mol ratio of n-BuLi) styrene 84g, and temperature is controlled
75 DEG C, Stress control under 0.25MPa, carry out the second polyreaction, polyase 13 records benzene second after 5 minutes
Alkene monomer conversion ratio reaches 97%；It is subsequently adding terminator isopropanol 0.118g and terminates reaction, and add monomer
The age resistor Irganox 1520 of weight 0.2%, then carries out devaporation desolventizing process to glue,
To olefin polymer J3, the molecular weight distribution of this olefin polymer J3 is tri-modal distribution, its concrete analysis
Test result is as shown in table 1.
Comparative example 1
This comparative example is for olefin polymer that reference is described and preparation method thereof.
The olefin polymer of reference is prepared according to the method for embodiment 1, except that, described coupling is anti-
Silicon chloride. (total coupling group of Silicon chloride. and the mol ratio of n-BuLi are 0.80:1) coupling in should
The consumption of agent is 0.380g, and be added without after coupling reaction terminates the styrene containing water carry out second gather
Close reaction, but be directly added into isopropanol and carry out terminating reaction, obtain reference olefin polymer DJ1, its
Analysis test result is as shown in table 1.
Comparative example 2
This comparative example is for olefin polymer that reference is described and preparation method thereof.
The olefin polymer of reference is prepared according to the method for embodiment 1, except that, in the first polymerization
Reaction adds 0.511g butyl lithium, is added without polyfunctional group coupling agent Silicon chloride., anti-in the second polymerization
Adding the styrene 372g not containing water in should, obtain reference olefin polymer DJ2, it analyzes test knot
Fruit is as shown in table 1.
Table 1
Test case
Test case is for illustrating the test of olefinic polymerization physical performance.
In 2 liters of stainless steel cauldrons with stirring, mass suspension method is used to prepare shock resistance polyphenyl second
Olefine resin.Specifically, it is firstly added 1232 grams of styrene, then is separately added into the olefin polymer of 70g
J1-J3 and reference olefin polymer DJ1-DJ2, is subsequently added into 70 grams of ethylbenzene, carries out after 28 grams of white oils
The bulk-suspension polymerization that radical initiator causes.Initiation reaction temperature is 110 DEG C, and initiator uses 1,1-
Diperoxy t-butylcyclohexane (DP-275B), initiator amount is 450ppm, and speed of agitator is 350
Rev/min.Respectively obtain MPS PS1-PS3 and DPS1-DPS2, in accordance with the following methods to it
Impact strength and glossiness are tested:
(1) impact strength: use U.S. CE AST company RESIL IMPACTOR instrument and according to
ASTM D256 standard testing, wherein, test temperature is 25 DEG C.Acquired results is as shown in table 2.
(2) surface gloss (45 °): use Switzerland's ZLR1050 vancometer and according to ASTM
D1003 standard testing, wherein, the numerical value of glossiness is the highest more good.Acquired results is as shown in table 2.
Table 2
| MPS | Olefin polymer | Impact strength (kJ/m2) | Glossiness |
| PS1 | J1 | 74 | 76 |
| PS2 | J2 | 74 | 74 |
| PS3 | J3 | 73 | 73 |
| DPS1 | DJ1 | 70 | 65 |
| DPS2 | DJ2 | 70 | 69 |
By the data of above-described embodiment and comparative example it can be seen that the alkene using the inventive method to obtain gathers
Compound has suitable Mooney viscosity (the Mooney viscosity ML at 100 DEG C1+4For 50-70), it is easy to follow-up
Processing, and there is suitable SV value (0.02-0.04Pa s), use the olefin polymer pair of the present invention
Resin is modified, and on the premise of the mechanical property ensureing resin, can be effectively improved the glossiness of resin.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. an olefin polymer, it is characterised in that described olefin polymer contains star-like conjugated diene
Hydrocarbon homopolymer, linear conjugated diene homopolymers and linear conjugated diene-monovinylarene copolymer,
The molecular weight distribution of described olefin polymer is tri-modal distribution, described olefin polymer door at 100 DEG C
Buddhist nun's viscosity ML1+4For 50-70, and the styrene solution of the described olefin polymer that concentration is 5 weight %
Viscosity at 25 DEG C is 0.02-0.04Pa s.
Olefin polymer the most according to claim 1, wherein, total with described olefin polymer
On the basis of weight, the content of described star-like conjugated diolefin homopolymerization thing is 40-55 weight %, described line style
The content of conjugated diolefin homopolymerization thing is 10-15 weight %, described linear conjugated diene-monovinylarene
The content of copolymer is 35-45 weight %.
Olefin polymer the most according to claim 1 and 2, wherein, with described olefin polymer
Gross weight on the basis of, monovinylarene in described linear conjugated diene-monovinylarene copolymer
The content of homopolymerization section is 20-40 weight %, and described monovinylarene homopolymerization section refers to described linear conjugated
Continuously containing six and more than six monovinylarenes on diene-monovinylarene copolymer strand
The content of construction unit；
Preferably, on the basis of the gross weight of described olefin polymer, described linear conjugated diene-mono-second
In alkenyl arene copolymer, the content of the micro-block of monovinylarene is 0-3 weight %, described mono-vinyl
The micro-block of aromatic hydrocarbons refers to contain continuously on described linear conjugated diene-monovinylarene copolymer strand
The content of five and less than five monovinylarene construction units.
Olefin polymer the most according to claim 1 and 2, wherein, with described olefin polymer
On the basis of the content of middle conjugated diene construction unit, in described conjugated diene construction unit 1,2-structure list
The content of unit is 5-15 weight %；
Preferably, in described olefin polymer on the basis of the content of conjugated diene construction unit, described
In conjugated diene construction unit, the content of cis-Isosorbide-5-Nitrae-construction unit is 25-40 weight %, anti-form-1, and 4-ties
The content of structure unit is 45-65 weight %.
Olefin polymer the most according to claim 1, wherein, described weight of otefi pi polymer
In distribution the peak molecular weight at three peaks according to retention time ascending be respectively 150,000-190,000,
100,000-150,000 and 50,000-60, the peak area percent at 000, three peaks according to retention time by little
It is respectively 40%-55%, 35%-45% and 10%-15% to big；Described weight of otefi pi polymer is distributed
In the molecular weight distributing index at three peaks be 1.05-1.2.
6. a preparation method for olefin polymer, wherein, the method includes:
(1) in an inert atmosphere, by single functionality organic lithium initiator and conjugated diene monomer
The first polyreaction is carried out in atent solvent；
(2) when conversion ratio >=97% of described conjugated diene monomer, by the first polymeric reaction product
Coupling reaction is carried out with polyfunctionality coupling agent；Total coupling group in described polyfunctionality coupling agent and institute
The mol ratio stating single functionality organic lithium initiator is 0.40-0.55:1；
(3) in the presence of terminator, the product that step (2) obtains is entered with mono vinyl arenes monomer
Row the second polyreaction so that the conversion ratio of described mono vinyl arenes monomer is >=97%；Described termination
Agent is 0.1-0.15:1 with the mol ratio of described single functionality organic lithium initiator.
Method the most according to claim 6, wherein, described polyfunctionality coupling agent is multifunctional
Degree halogenide, preferably methyl trifluoro SiClx, methyl trichlorosilicane, methyl tribromo SiClx, methyl triiodo
SiClx, methyl trifluoro stannum, tin methyltrichloride, methyl tribromide stannum, methyl triiodide stannum, butyl
Trifluoro SiClx, butyl trichlorosilicane, butyl tribromo SiClx, butyl triiodo SiClx, Silicon fluoride., tetrachloro
SiClx, Silicon bromide., silicon tetraiodide, tin tetrafluoride, butter of tin, tin tetrabromide, tin tetraiodide,
At least one in butter of tin, butter of tin, more preferably Silicon chloride. and/or butter of tin, optimum
Elect Silicon chloride. as.
8. according to the method described in claim 6 or 7, wherein, relative to the conjugation of 100 weight portions
Diolefinic monomer, the consumption of described mono vinyl arenes monomer is 20-40 weight portion, preferably 25-35
Weight portion.
9. according to the method described in claim 6 or 7, wherein, the method is additionally included in step (1)
Middle addition structure regulator and/or gel inhibitor；
Preferably, described structure regulator is in nitrogenous, oxygen-containing, sulfur-bearing, phosphorous polar compound
At least one, preferably ether, butyl oxide, dioxane, oxolane, glycol dimethyl ether,
Two dry diethylene glycol dimethyl ethers, diphenyl ether, triethylamine, tetramethylethylenediamine, HMPA, the tert-butyl alcohol
At least one in potassium, sodium alkyl benzene sulfonate and ethyl tetrahydrofurfuryl ether, more preferably oxolane and/
Or ethyl tetrahydrofurfuryl ether；
Preferably, described gel inhibitor is selected from 1，2-butadiene, tertiary amoxy potassium/Silicon chloride., tetramethyl
At least one in base ethylenediamine/1,2-butadiene and THF/1,2-butadiene.
10. according to the method described in claim 6 or 7, wherein, the condition of described first polyreaction
Including: temperature is 40-130 DEG C, and pressure is 0.1-1.5MPa, and the time is 10-70 minute；
Preferably, the condition of described coupling reaction includes: temperature is 40-130 DEG C, and pressure is
0.1-1.5MPa, the time is 20-70 minute；
Preferably, the condition of described second polyreaction includes: temperature is 40-130 DEG C, and pressure is
0.1-1.5MPa, the time is 20-70 minute.
11. olefin polymers prepared by the method described in any one in claim 6-10.
In 12. claim 1-5 and 11, the olefin polymer described in any one is as polystyrene tree
The application of the modifying agent of fat and/or acrylonitrile-butadiene-styrene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026493.0A CN105860407B (en) | 2015-01-20 | 2015-01-20 | A kind of olefin polymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026493.0A CN105860407B (en) | 2015-01-20 | 2015-01-20 | A kind of olefin polymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105860407A true CN105860407A (en) | 2016-08-17 |
| CN105860407B CN105860407B (en) | 2018-05-11 |
Family
ID=56622796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510026493.0A Active CN105860407B (en) | 2015-01-20 | 2015-01-20 | A kind of olefin polymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105860407B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251263A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
| CN109251262A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
| CN114316139A (en) * | 2020-09-30 | 2022-04-12 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482677A (en) * | 1980-08-25 | 1984-11-13 | Japan Elastomer Co., Ltd. | Process for producing high impact polystyrene |
| JPS60104111A (en) * | 1983-11-11 | 1985-06-08 | Asahi Chem Ind Co Ltd | Impact-resistant polystyrene resin and its production |
| CN1260806A (en) * | 1997-08-13 | 2000-07-19 | 陶氏化学公司 | High-gloss high-impact monovinylidene aromatic polymers |
| CN1348474A (en) * | 1999-02-09 | 2002-05-08 | 陶氏化学公司 | High impact monovinylidene aromatic polymers |
| JP2004307841A (en) * | 2003-03-27 | 2004-11-04 | Ps Japan Corp | Rubber-modified styrenic resin excellent in weather resistance and impact resistance, its production process and laminate obtained by using the resin |
| CN1640898A (en) * | 2004-01-08 | 2005-07-20 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method for preparing low cis-polybutadiene by stepwise excitation |
| CN102532377A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber as well as preparation method and application thereof |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
| CN103709332A (en) * | 2008-12-16 | 2014-04-09 | 维尔萨利斯股份公司 | Rubber-reinforced vinyl aromatic (co) polymer, having an optimum balance of physic-mechanical properties and a high gloss |
-
2015
- 2015-01-20 CN CN201510026493.0A patent/CN105860407B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4482677A (en) * | 1980-08-25 | 1984-11-13 | Japan Elastomer Co., Ltd. | Process for producing high impact polystyrene |
| JPS60104111A (en) * | 1983-11-11 | 1985-06-08 | Asahi Chem Ind Co Ltd | Impact-resistant polystyrene resin and its production |
| CN1260806A (en) * | 1997-08-13 | 2000-07-19 | 陶氏化学公司 | High-gloss high-impact monovinylidene aromatic polymers |
| CN1348474A (en) * | 1999-02-09 | 2002-05-08 | 陶氏化学公司 | High impact monovinylidene aromatic polymers |
| JP2004307841A (en) * | 2003-03-27 | 2004-11-04 | Ps Japan Corp | Rubber-modified styrenic resin excellent in weather resistance and impact resistance, its production process and laminate obtained by using the resin |
| CN1640898A (en) * | 2004-01-08 | 2005-07-20 | 中国石油化工股份有限公司北京燕山分公司研究院 | Method for preparing low cis-polybutadiene by stepwise excitation |
| CN103709332A (en) * | 2008-12-16 | 2014-04-09 | 维尔萨利斯股份公司 | Rubber-reinforced vinyl aromatic (co) polymer, having an optimum balance of physic-mechanical properties and a high gloss |
| CN102532377A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber as well as preparation method and application thereof |
| CN103030756A (en) * | 2011-10-10 | 2013-04-10 | 中国石油化工股份有限公司 | Styrene-butadiene copolymer as well as preparation and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李建成等: "PS系列树脂的增韧机理及性能影响因素", 《弹性体》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251263A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
| CN109251262A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof |
| CN109251263B (en) * | 2017-07-14 | 2021-02-05 | 中国石油化工股份有限公司 | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof |
| CN114316139A (en) * | 2020-09-30 | 2022-04-12 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
| CN114316139B (en) * | 2020-09-30 | 2024-03-01 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105860407B (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102532377B (en) | Low cis-polybutadiene rubber as well as preparation method and application thereof | |
| Morton et al. | Synthesis and Properties of Uniform Polyisoprene Networks. I. Synthesis and Characterization of α, ω-Dihydroxy-Polyisoprene | |
| CN1215402A (en) | Compound containing nitroxyl | |
| CN109485791A (en) | Linear butylbenzene copolymer and preparation method thereof and composition and aromatic vinyl resin and preparation method thereof | |
| CN105860407A (en) | Olefin polymer, preparation method and application thereof | |
| CN108136827A (en) | Include the rubber composition of the diene elastomer in the middle part of chain with functional group | |
| JP4213468B2 (en) | Star-block interpolymers and their manufacture | |
| KR20050021458A (en) | Coupled styrenic block copolymers and process for preparing same | |
| CN1745116A (en) | Conjugated diene polymers and copolymer blocks and process for preparing same | |
| KR20200064569A (en) | A composition for seeded polymerization, a seed copolymer and a method for preparing the same | |
| US10315463B2 (en) | Method for synthesising a polymer having a hydroxyaryl group, product obtained using said method and composition containing same | |
| RU2626967C2 (en) | Method for producing 1,4-cis-polybutadiene | |
| US6777499B2 (en) | Multiblock interpolymers and processes for the preparation thereof | |
| CN105860406B (en) | A kind of olefin polymer and its preparation method and application | |
| CN110105498A (en) | One kind is suitable for single silicon hydrogen functionalization star polymer and preparation method thereof of Si―H addition reaction chemical reaction | |
| CN104558456B (en) | Block copolymer, block copolymer composition, vulcanized rubber, application of block copolymer, block copolymer composition and vulcanized rubber and block copolymer preparation method | |
| CN104628896B (en) | Method for improving coupling efficiency of solution polymerized styrene-butadiene rubber | |
| CN106928416A (en) | Monovinylarene-conjugated diene copolymer and preparation method and random linear copolymer and composition and vulcanized rubber and application | |
| CN107286296A (en) | A kind of application of butadiene-b- isoprene copolymers | |
| CN110128607A (en) | Monovinylarene-conjugated diene block copolymer and block copolymer composition and vulcanized rubber and its application | |
| EP1266916B1 (en) | Multiblock copolymer and the preparing method thereof | |
| CN101168588B (en) | Crystallization-amorphism-crystallization stereo triblock polybutadiene and preparation method thereof | |
| JP6426888B2 (en) | Branching material, method for producing polymer composition and polymer composition | |
| CN107540890A (en) | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application | |
| CN106256843B (en) | A kind of olefin copolymer and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |