CN110294869A - Polybutadiene and preparation method thereof and vulcanizate - Google Patents
Polybutadiene and preparation method thereof and vulcanizate Download PDFInfo
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Abstract
The present invention relates to polybutadiene, and in particular, to polybutadiene and preparation method thereof and vulcanizate.The polybutadiene contains: high-cis polybutadiene, branching type polybutadiene and rule 1,2- polybutadiene；It wherein, is 92 weight % or more along the content of Isosorbide-5-Nitrae-paradigmatic structure in the high-cis polybutadiene；The main chain of the branching type polybutadiene be high-cis paradigmatic structure and branch be between advise 1,2- paradigmatic structure；The content of suitable 1,4- paradigmatic structure is 92 weight % or more in the main chain；The content of 1,2- paradigmatic structure is 85 weight % or more in the branch；The content of 1,2- paradigmatic structure is 85 weight % or more in described rule 1,2- polybutadiene, and the crystallinity that 1,2- polybutadiene is advised between described is 10% or more.In polybutadiene provided by the invention, rule 1,2- polybutadiene and high-cis polybutadiene have good compatibility, and thus obtained vulcanizate has excellent stress at definite elongation.
Description
Technical field
The present invention relates to polybutadiene, and in particular, to polybutadiene and preparation method thereof and vulcanizate.
Background technique
Polybutadiene rubber is the second-biggest-in-the-world synthetic rubber kind for being only second to butadiene-styrene rubber.The poly- fourth of whole world commercialization
Diene rubber is different according to initiation/catalyst type, can be divided into lithium system, nickel system, titanium system, cobalt system and rare-earth system (neodymium series) five
Class.The polybutadiene that preparation causes in lithium system is low cis (cis- Isosorbide-5-Nitrae structural content is usually 40% or so), is commonly used in plastics
It is modified to use, it is impossible to be used in manufacture tire.Prepared by nickel system, titanium system, cobalt system and rare-earth system catalysis is that cis- 1,4 structural content is big
In 90% high-cis polybutadiene, there is excellent elasticity, wearability, cold resistance, flexible resistance and good dynamic property,
It is usually used in the positions such as tyre surface, sidewall and the tire shoulder of tire.China builds up 10,000 tons production early in Yu Beijing Yan Hua company in 1971
Device is simultaneously gone into operation, and the national production technology organized through 1973 to 1975 Nian Youyuan burning portions, which is tackled key problems, joins in a battle, and forms China
The nickel system high-cis polybutadiene production technology of characteristic.After unremitting effort in more than 50 years, nickel system, China high-cis polybutadiene
Production technology has reached the world in the various aspects such as product quality, consumption of raw materials, reactor production capacity, ancillary engineering facility and has first intake
It is flat.21 century is entered, our sequentially operation Rare Earth high-cis polybutadienes again enrich high-cis polybutadiene kind.
So far, Chinese high-cis polybutadiene product has broken through million tons/year, is that the big high-cis polybutadiene of the first in the world is raw
Produce state.
With social progress and energy-saving and environment-friendly requirement, automotive light weight technology becomes a popular research direction.For Gao Shun
It, can be raw using less rubber if its vulcanizate stress at definite elongation can be obviously improved for formula polybutadiene
The tire that output is met the requirements, so that tire thickness (especially sidewall position) is reduced.In this way, on the one hand can reduce using rubber
The usage amounts such as glue, reinforcing agent, vulcanizing agent, reduce production cost；On the other hand tire weight is alleviated, plays saving automobile
The effect of the energy.
Using the catalyst systems Butadiene Polymerization such as iron, cobalt and molybdenum, 1,2- polybutadiene is advised between can synthesizing.It is this
Between advise 1,2- polybutadiene and can crystallize at normal temperature, when crystallinity is lower than 10%, still there are rubber properties；Crystallinity is higher than
It when 35%, then follows the string, shows plastic nature；At 25% or so, performance belongs to crystallinity between rubber and plastics
Thermoplastic elastomer (TPE).Be blended in high-cis polybutadiene it is a small amount of between advise 1,2- polybutadiene, vulcanizate can be improved and determine to stretch
The performances such as stress, tensile strength and tearing strength, additional amount are advisable with 8%.When additional amount is excessive, performance declines instead.This is main
It is to be blended since rule 1,2- polybutadiene and high-cis polybutadiene have very big difference on microstructure and properties
System belongs to the bad system of mutual compatibility, therefore a small amount of be added is conducive to improve performance, and is excessively added, and instead results in performance change
Difference.
Summary of the invention
It is an object of the invention to overcome existing rule 1,2- polybutadiene and high-cis polybutadiene mutual compatibility bad
The problem of, provide inter-species rule 1,2- polybutadiene good polybutadiene compatible with high-cis polybutadiene and its preparation side
Method and vulcanizate.
To achieve the goals above, one aspect of the present invention provides a kind of polybutadiene, which contains: high-cis is poly-
Butadiene, branching type polybutadiene and rule 1,2- polybutadiene；
Wherein, on the basis of the weight of the high-cis polybutadiene, along Isosorbide-5-Nitrae-polymerization in the high-cis polybutadiene
The content of structure is 92 weight % or more；
The main chain of the branching type polybutadiene be high-cis paradigmatic structure and branch be between advise 1,2- paradigmatic structure；With institute
On the basis of the weight for stating main chain, the content of suitable Isosorbide-5-Nitrae-paradigmatic structure is 92 weight % or more in the main chain；With the weight of the branch
On the basis of amount, the content of 1,2- paradigmatic structure is 85 weight % or more in the branch；
On the basis of weight to advise 1,2- polybutadiene between described, 1,2- paradigmatic structure in 1,2- polybutadiene is advised between described
Content be 85 weight % or more, advised between described 1,2- polybutadiene crystallinity be 10% or more.
Second aspect of the present invention provides a kind of preparation method of polybutadiene, this method comprises:
In organic solvent, in the presence of nickel catalyst and water, butadiene and rule 1, a 2- polybutadiene are gathered
Reaction is closed, the temperature of the polymerization reaction is 50 DEG C or more；
Wherein, on the basis of the weight to advise 1,2- polybutadiene between described, it is poly- that 1,2- in 1,2- polybutadiene is advised between described
The content for closing structure is 85 weight % or more, and the crystallinity that 1,2- polybutadiene is advised between described is 10% or more；
The nickel catalyst contains component A, component B and component C；
Component A: carboxylic acid nickel class compound；
Component B: trialkylaluminium；
Component C: fluorochemical；
Wherein, the molar ratio of component B and component C are 0.2-0.35:1, and the molar ratio of water and component C are 0.2-0.5:1.
Third aspect present invention provides polybutadiene prepared by the above method.
Fourth aspect present invention, which is provided, is vulcanized vulcanizate obtained by above-mentioned polybutadiene.
In polybutadiene provided by the invention, rule 1,2- polybutadiene has good compatible with high-cis polybutadiene
Property, thus obtained vulcanizate has excellent stress at definite elongation.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of polybutadiene, which contains: the poly- fourth of high-cis polybutadiene, branching type
Diene and rule 1,2- polybutadiene；
Wherein, on the basis of the weight of the high-cis polybutadiene, along Isosorbide-5-Nitrae-polymerization in the high-cis polybutadiene
The content of structure is 92 weight % or more；
The main chain of the branching type polybutadiene be high-cis paradigmatic structure and branch be between advise 1,2- paradigmatic structure；With institute
On the basis of the weight for stating main chain, the content of suitable Isosorbide-5-Nitrae-paradigmatic structure is 92 weight % or more in the main chain；With the weight of the branch
On the basis of amount, the content of 1,2- paradigmatic structure is 85 weight % or more in the branch；
On the basis of weight to advise 1,2- polybutadiene between described, 1,2- paradigmatic structure in 1,2- polybutadiene is advised between described
Content be 85 weight % or more, advised between described 1,2- polybutadiene crystallinity be 10% or more.
According to the present invention, polybutadiene of the invention be equivalent to containing high-cis polybutadiene, branching type polybutadiene and
Between advise 1,2- polybutadiene a kind of polybutadiene product mixture.Wherein, the presence of branching type polybutadiene, can be significantly
The compatibility for improving high-cis polybutadiene and rule 1,2- polybutadiene, advises 1,2- polybutadiene and is distributed evenly between promotion
In high-cis polybutadiene, thus between advise 1,2- polybutadiene convenient for equably tying in the distributed point of high-cis polybutadiene
Crystalline substance plays the role of " physical crosslinking point ", to substantially improve high-cis polybutadiene cold flow properties, green strength and mixing
Glue intensity is conducive to production engineering tire and aircraft tyre.In particular, during forming vulcanizate, it should " physical crosslinking
Point " is crosslinked with high-cis polybutadiene segment or is crosslinked mutually, in final polybutadiene vulcanizate network by sulfurization
Middle formation equally distributed " chemical crosslinking point ", to assign polybutadiene vulcanizate excellent performance, especially stress at definite elongation
It significantly improves.
Wherein, the content of the high-cis polybutadiene, branching type polybutadiene and rule 1,2- polybutadiene can be
It is changed in wider range, it is preferable that on the basis of the weight of the polybutadiene, the branching type polybutadiene and rule 1,2-
The total content of polybutadiene is 5-25 weight %, and the content of the branching type polybutadiene is 1-20 weight %, and the high-cis is poly-
The content of butadiene is 75-95 weight %.It is highly preferred that on the basis of the weight of the polybutadiene, the branching type polybutadiene
The total content of alkene and rule 1,2- polybutadiene is 10-25 weight %, and the content of the branching type polybutadiene is 5-20 weight %,
The content of the high-cis polybutadiene is 75-90 weight %.
According to the present invention, it is well known that the polybutadiene configuration unit usually has 3 kinds of stereoregular structures, i.e., along 1,
4- paradigmatic structure, anti-Isosorbide-5-Nitrae-paradigmatic structure and 1,2- paradigmatic structure, wherein 1,2- paradigmatic structure again can be vertical with atactic, isotactic
Three kinds of spatial configurations of structure and syndiotactic exist.In the present invention, although along Isosorbide-5-Nitrae-paradigmatic structure in the high-cis polybutadiene
Content meet 92 weight % or more and can meet requirement of the present invention to high-cis polybutadiene, it is preferable that with the high-cis
On the basis of the weight of polybutadiene, the content of suitable Isosorbide-5-Nitrae-paradigmatic structure is 95 weight % or more in the high-cis polybutadiene.And
Anti- Isosorbide-5-Nitrae-paradigmatic structure and 1 in high-cis polybutadiene, the content of 2- paradigmatic structure is then less, wherein anti-Isosorbide-5-Nitrae-polymerization knot
The content of structure for example can be 0-3 weight %, preferably 0-1.5 weight %；The content of 1,2- paradigmatic structure can be for example 0-2 weight
Measure %, preferably 0-1 weight %.Preferably, the number-average molecular weight of the high-cis polybutadiene is 50,000-150,000, molecule
Amount profile exponent is 2.8-4.0.
According to the present invention, between the branching type polybutadiene is actually on the side chain graft of the high-cis polybutadiene
Advise 1,2- polybutadiene.Wherein, under preferable case, in the branching type polybutadiene, on the basis of the weight of the main chain, institute
The content for stating suitable 1,4- paradigmatic structure in main chain is 95 weight % or more；On the basis of the weight of the branch, 1 in the branch,
The content of 2- paradigmatic structure is 90 weight % or more (for example, 90-95 weight %).Wherein, anti-Isosorbide-5-Nitrae-paradigmatic structure and 1 of main chain,
The content of 2- paradigmatic structure is then less, their content can be with reference to above to the associated description of high-cis polybutadiene.Side
The content of suitable Isosorbide-5-Nitrae-paradigmatic structure and anti-Isosorbide-5-Nitrae-paradigmatic structure in chain is less, wherein the content of suitable Isosorbide-5-Nitrae-paradigmatic structure is for example
It can be 0-6 weight %, preferably 0-3 weight %；The content of anti-Isosorbide-5-Nitrae-paradigmatic structure for example can be 0-6 weight %, preferably 0-
3 weight %.
In the case of, according to the invention it is preferred to, on the basis of the weight to advise 1,2- polybutadiene between described, 1,2- is advised between described
The content of 1,2- paradigmatic structure is 90 weight % or more (for example, 90-95 weight %) in polybutadiene, and the poly- fourth of 1,2- is advised between described
The crystallinity of diene is 10-40%, preferably 12-30%, more preferably 20-30%.Preferably, 1,2- polybutadiene is advised between described
Number-average molecular weight be 30,000-100,000.Wherein, this advises suitable Isosorbide-5-Nitrae-paradigmatic structure and anti-1 in 1,2- polybutadiene,
The content of 4- paradigmatic structure is less, wherein the content along Isosorbide-5-Nitrae-paradigmatic structure for example can be 0-6 weight %, preferably 0-3 weight
Measure %；The content of anti-Isosorbide-5-Nitrae-paradigmatic structure for example can be 0-6 weight %, preferably 0-3 weight %.
In the case of, according to the invention it is preferred to, the crude rubber Mooney viscosity ML of the polybutadiene(1+4)100 DEG C are 40-70, excellent
It is selected as 40-50.
Second aspect of the present invention provides a kind of preparation method of polybutadiene, this method comprises:
In organic solvent, in the presence of nickel catalyst and water, butadiene and rule 1, a 2- polybutadiene are gathered
Reaction is closed, the temperature of the polymerization reaction is 50 DEG C or more；
Wherein, on the basis of the weight to advise 1,2- polybutadiene between described, it is poly- that 1,2- in 1,2- polybutadiene is advised between described
The content for closing structure is 85 weight % or more, and the crystallinity that 1,2- polybutadiene is advised between described is 10% or more；
The nickel catalyst contains component A, component B and component C；
Component A: carboxylic acid nickel class compound；
Component B: trialkylaluminium；
Component C: fluorochemical；
Wherein, the molar ratio of component B and component C are 0.2-0.35:1, and the molar ratio of water and component C are 0.2-0.5:1.
According to the present invention, the present invention, will be so that polymerizing butadiene obtains the poly- fourth of high-cis under the catalysis of nickel catalyst
Diene, and the addition of rule 1,2- polybutadiene, can make the side group double bond for advising 1,2- polybutadiene between part open, thus
It is grafted in the high-cis polybutadiene of part and forms the branching type polybutadiene.
Wherein, 1,2- polybutadiene is advised between described can obtain in such a way that this field is conventional, such as can be commercially available
Product can also be made using the conventional method of this field, as long as advising 1 between described, 2- polybutadiene meets, to advise 1,2- between described
On the basis of the weight of polybutadiene, the content that 1,2- paradigmatic structure in 1,2- polybutadiene is advised between described is 85 weight % or more, institute
The crystallinity that 1,2- polybutadiene is advised between stating is 10% or more.Under preferable case, to advise 1,2- polybutadiene between described
On the basis of weight, the content that 1,2- paradigmatic structure in 1,2- polybutadiene is advised between described is 90 weight % or more (for example, 90-95
Weight %), the crystallinity that 1,2- polybutadiene is advised between described is 10-40%, preferably 12-30%, more preferably 20-30%.It is preferred that
Ground, the number-average molecular weight that 1,2- polybutadiene is advised between described is 30,000-100,000.Other, which can refer to, above advises in relation between
The description of 1,2- polybutadiene.
In the case of, according to the invention it is preferred to, the weight ratio of rule 1,2- polybutadiene and butadiene is 0.04-0.32:1.
According to the present invention, rule 1, a 2- polybutadiene adding manner can be added for powder or wiring solution-forming is added in advance,
It is preferred that preparatory wiring solution-forming is added.When preparatory wiring solution-forming, solvent can be inert to catalyst components organic from selecting
Solvent, conventional can choose one of naphthane, methylene chloride, benzene,toluene,xylene etc. or a variety of.Between used
The concentration for advising the solution of 1,2- polybutadiene for example can be 5-15 weight %.
According to the present invention, the organic solvent can be any hydrocarbon solvent inert to catalyst, the organic solvent
It such as can be C5-C10Alkane, C5-C10Cycloalkane and C6-C12One of aromatic hydrocarbons or a variety of, preferably hexane, hexamethylene,
One of heptane, pentane, isopentane, octane, hexahydrotoluene, benzene,toluene,xylene and isopropylbenzene are a variety of.Wherein, institute
The dosage for stating organic solvent can change in a wider range, it is preferable that described organic relative to the butadiene of 100 parts by weight
The dosage of solvent is 300-2000 parts by weight.Wherein, butadiene provides preferably in the form of its solution, such as can be by butadiene
The solution of butadiene is formed with the organic solvent, thus butadiene and organic solvent are provided.
Catalyst of the present invention is nickel catalyst and also needs that there are certain water content.According to the present invention, it sends out
Bright people has found that, in order to obtain the required polybutadiene of the present invention, preparation method must control 3 by lot of experiments
Key point:
(1) component B and component C molar ratio must be controlled in B:C=0.2-0.35:1, when molar ratio is lower than 0.2, catalyst
Activity is very low or inactive, and polymerization reaction cannot proceed normally；When molar ratio is higher than 0.35, branching reaction is suppressed, basic
Less than branching type polybutadiene；
(2) water and component C molar ratio must be controlled in H2O:C=0.2-0.5:1, when molar ratio is lower than 0.2, catalyst is living
Property is very low or inactive, and polymerization reaction cannot proceed normally；When molar ratio is higher than 0.5, branching reaction is suppressed, and cannot get substantially
Branching type polybutadiene；
(3) temperature of polymerization reaction must be at 50 DEG C or more, when being lower than 50 DEG C, and branching reaction is suppressed, and cannot get substantially
Branching type polybutadiene.
Wherein, under preferable case, the molar ratio of the component A and component B are 1:3-10.Preferably, the component B and group
The molar ratio for dividing C is 0.2-0.3:1.Preferably, the molar ratio of water and component C are 0.2-0.3:1.
It according to the present invention, is the major catalyst of the nickel catalyst, nickel element as the carboxylic acid nickel class compound of component A
For activated centre metallic atom.Preferably, the carboxylic acid nickel class compound be nickel naphthenate, caproic acid nickel, enanthic acid nickel, nickel octoate,
N-nonanoic acid nickel and capric acid nickel, preferably nickel naphthenate and/or nickel octoate.
According to the present invention, it is co-catalyst as the trialkylaluminium of component B, primarily serves and restore inactive nickelous
At the effect of active monovalence nickel or zero-valent nickel.Preferably, the trialkylaluminium is by formula Al (R)3Represented, R is selected from C1-
C6Alkyl；It is highly preferred that the trialkylaluminium be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl aluminium,
Three base aluminium and triisobutyl aluminiums, preferably triisobutyl aluminium.
According to the present invention, the fluorochemical as component C provides fluorine element for catalyst active center, is indispensable
One of component.Preferably, the fluorochemical is one kind or more of hydrogen fluoride, boron trifluoride and boron trifluoride complex
Kind.Wherein, the specific example of the boron trifluoride complex for example can be boron trifluoride etherate, boron trifluoride butyl ether
One of complex compound etc. is a variety of.Fluorochemical of the invention is preferably boron trifluoride complex, and thus more preferably three
It is fluorinated diethyl etherate and/or boron trifluoride ether complex.
According to the present invention, water is also one of indispensable component, in the presence of anhydrous, catalyst can not Butadiene it is poly-
It closes, when water excess can then destroy catalyst, cause catalyst activity lower or inactive.In the present invention, the source of water includes outer
Add minor amount of water contained in the raw materials such as water and solvent, butadiene, component A, component B, component C.
In accordance with the present invention it is preferred that the component A, component B and component C are respectively provided in the form of its solution, used
Solvent be each independently selected from C5-C10Alkane, C5-C10Cycloalkane and C6-C12One of aromatic hydrocarbons or a variety of, preferably penta
One of alkane, pentamethylene, hexane, hexamethylene, hexahydrotoluene, heptane, octane, benzene,toluene,xylene and isopropylbenzene are more
Kind.
Wherein, the concentration for providing the solution of component A can be for example 0.01-0.5mol/L, provide the dense of the solution of component B
Degree can be for example 0.05-0.5mol/L, and the concentration for providing the solution of component C for example can be 0.01-0.5mol/L.
According to the present invention, the nickel catalyst can be provided in reaction system each independently, can also mix each other
It is re-introduced into after conjunction into reaction system, the present invention preferably first mixes component A and component B, and gained mixture and component C are not mixed
Under be introduced in reaction system.
According to the present invention, the dosage of the nickel catalyst can be suitably adjusted according to required polybutadiene,
Such as the nickel catalyst makes the number-average molecular weight of resulting high-cis polybutadiene be 50,000-150,000, molecular weight
Profile exponent is 2.8-4.0.Preferably, relative to the butadiene of 1mol, the dosage of the nickel catalyst makes the use of component A
Amount is 50-1000 μm of ol, preferably 100-800 μm of ol.
In the case of, according to the invention it is preferred to, the condition of the polymerization reaction includes: that temperature is 50-100 DEG C, and the time is
0.5-5h.It is highly preferred that it is 60-100 DEG C that the condition of the polymerization reaction, which includes: temperature, time 1.5-3h.
It is according to the present invention, to be polymerized the polymerization reaction to be terminated, and introduce antioxidant after reaction,
It can not also terminate, be introduced directly into antioxidant.
Wherein, terminating can be terminated using the terminator of this field routine, which for example can be for C1-C4's
One of alcohol, organic acid etc. are a variety of, preferably in methanol, ethyl alcohol, propyl alcohol, isopropanol, the tert-butyl alcohol, stearic acid and citric acid
It is one or more.
Wherein, the antioxidant for example can be antioxidant 1010, antioxidant 1076, antioxidant 164, irgasfos 168, resist
At least one of oxygen agent 264, antioxidant 1520 etc..The content of the antioxidant can change in a wider range, relative to 100
Total dosage of the butadiene of parts by weight and rule 1,2- polybutadiene, the dosage of the antioxidant is preferably 0.1-1 parts by weight.
According to the present invention, in order to extract polymer, method of the invention further includes, by the product after termination
It is precipitated using the alcohol of C1-C4, so that polymer is precipitated out, then separating, washing, or using commonly used in the art
The mode of hot water cohesion, can be obtained polybutadiene of the invention.
It should be understood that the polybutadiene it is as described above polybutadiene it is the same, contain the Gao Shun
Formula polybutadiene, the branching type polybutadiene and it is described between advise 1,2- polybutadiene, for details, reference can be made to correlations above to retouch
It states, details are not described herein by the present invention.
Wherein, the measurement of mentioned component content is carried out using following methods in the polybutadiene: by product (quality
For m0) with after hexane extraction 72 hours, the available component for being dissolved in hexane and the component insoluble in hexane.It is dissolved in the group of hexane
It is divided into high-cis polybutadiene, the mixture of 1,2- polybutadiene and branching type polybutadiene is advised between being insoluble in hexane component,
Constituent mass insoluble in hexane is m1.In the present invention, m1The quality m of 1,2- polybutadiene is advised between being added greater than reaction2,
This is the reason for having branching type polybutadiene to generate.The then total mass fraction of branching type polybutadiene and rule 1,2- polybutadiene
It can be calculated according to formula (1), the mass fraction of branching type polybutadiene can be calculated according to formula (2).
The total mass fraction of branching type polybutadiene and rule 1,2- polybutadiene:
m1/m0× 100% (1)
The mass fraction of branching type polybutadiene:
[(m1-m2)/Mn1]×(Mn1+Mn2)/m0× 100% (2)
In formula (2), Mn1For be dissolved in hexane component number-average molecular weight (i.e. the number-average molecular weight of high-cis polybutadiene),
Mn2For a number-average molecular weight for rule 1,2- polybutadiene.
Third aspect present invention provides polybutadiene prepared by the above method.
The polybutadiene is as described above, and details are not described herein by the present invention.
Fourth aspect present invention, which is provided, is vulcanized vulcanizate obtained by above-mentioned polybutadiene.
According to the present invention, the vulcanizate being prepared using the polybutadiene with above structure feature can have preferably
Mechanical property.The vulcanization can be the sulfurization technology that this field routinely uses, such as side documented by GB/T8660-2008
Method.Sulfidation can use mill mixing, be vulcanized to obtain vulcanizate after mixing.It is kneaded and the condition of vulcanization can be
Conventional use of condition, such as melting temperature can be 40-200 DEG C, and mixing time can be 10-60min；Curing temperature can be with
It is 100-200 DEG C, vulcanization time can be 10-80min.
Vulcanizate mechanical property with higher provided by the invention, 200% stress at definite elongation of the especially described vulcanizate are
7.2MPa or more, preferably 12-16MPa.Tire is produced using polybutadiene provided by the invention and its vulcanizate as a result, it can
To reduce tire thickness, especially sidewall part thickness；On the one hand tire production cost can be reduced, on the other hand plays section
The about effect of energy source of car.
The present invention will be described in detail by way of examples below.
In following example:
The molecular weight and molecualr weight distribution of hexane soluble fraction produces HLC-8320 type gel permeation chromatograph using Tosoh
(GPC) it measures, THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 40 DEG C.The molecular weight of the insoluble part of hexane is adopted
GPC220 type gel permeation chromatograph (GPC) measurement is produced with PL company, chloroform is mobile phase, and Narrow distribution polystyrene is mark
Sample, temperature are 30 DEG C.
Crystallinity produces Q200 type differential scanning calorimeter using TA company and measures.
Suitable 1,4- paradigmatic structure, anti-1,4- paradigmatic structure and the 1,2- paradigmatic structure of polybutadiene use ThermoFisher
Nicolet IS5 type infrared spectrometer is with hot value measured by pressed film method.
Mooney viscosity is measured using the SMV-201SK-160 type of Japanese Shimadzu Corporation's production without rotor Mooney viscosity instrument,
In, preheating time 1min, rotation time 4min, test temperature are 100 DEG C.
200% stress at definite elongation measures with the following method: by rubber be added in mixer (BR1600, Britain farad you) in
It plasticates at 60 DEG C 30 seconds, the filler in addition to sulphur and promotor is then added, when the temperature of sizing material reaches 170 DEG C or total time
It discharges after reaching 5min；Park 4 hours, then add to again and be kneaded 30 seconds in mixer at 40 DEG C, be added later sulphur and
Sulphur promotor discharges after being kneaded 240 seconds.Then (X (S) K-160 type, Shanghai Shuan Yi rubber and plastics machine factory) is longitudinal in open mill
Thin to lead to 3 bottom sheet, open mill roller is room temperature.Each material additional proportion is determined according to GB/T 8660-2008.Last gained sizing material
Vulcanize at 145 DEG C, the optimum cure that vulcanization time is measured according to no rotor vulcameter (GT-M2000-A type, the high Inland Steel in Taiwan)
Time tc90 determines.The dumbbell shape test sample for determining 2mm thickness after vulcanization with cut-off knife, using Material Testing Machine (SHIMADZU,
AG-20KNG it) is tested according to GB/T528-2009.
Preparation example 1
Will between advise 1,2- polybutadiene (purchased from the RB810 of JSR company, 1,2- paradigmatic structure content is 90.2 weight %,
Crystallinity is 14.2%, and number-average molecular weight is the 5.2 solution sPB-1 that 10 weight % ten thousand) are formulated as using dimethylbenzene, and solution water number is
34μg/g。
Preparation example 2
Will between advise 1,2- polybutadiene (purchased from the RB830 of JSR company, 1,2- paradigmatic structure content is 93.3 weight %,
Crystallinity is 28.7%, and number-average molecular weight is the 4.7 solution sPB-2 that 10 weight % ten thousand) are formulated as using dimethylbenzene, and solution water number is
32μg/g。
Catalyst preparation example 1
Under nitrogen protection, the hexane solution and 21mL concentration for the nickel naphthenate for being 0.07mol/L by 5mL concentration be
The hexane solution of the triisobutyl aluminium of 0.1mol/L mixes and in 30 DEG C of ageing 20min, obtains ageing liquid Ni-Al-1, wherein
The molar ratio of Al/Ni is 6:1.
Catalyst preparation example 2
Under nitrogen protection, the hexane solution and 28mL concentration for the nickel naphthenate for being 0.07mol/L by 5mL concentration be
The hexane solution of the triisobutyl aluminium of 0.1mol/L mixes and in 30 DEG C of ageing 15min, obtains ageing liquid Ni-Al-2, wherein
The molar ratio of Al/Ni is 8:1.
Catalyst preparation example 3
Under nitrogen protection, using hexane, (boron trifluoride etherate is diluted 500 times of (bodies for 16 μ g/mL) by water number
Product ratio), obtained solution BF3-1。
Embodiment 1
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
Under nitrogen protection, by the hexane solution of the butadiene of the 14.09 weight % of 58.2g (water number be 22 μ g/g) and
The sPB-1 of 6.5g is mixed, and the BF of the Ni-Al-1 and 22.9mL of 1.1mL is then added3- 1(wherein, H2O:BF3Molar ratio is
0.27, rule 1,2- polybutadiene: the weight ratio of butadiene is 0.08, Ni: butadiene molar ratio is 1.0 × 10-4, triisobutyl
Aluminium: BF3Molar ratio be 0.25), and at 60 DEG C carry out polymerization reaction 3h, then be added antioxidant 264 ethanol solution (concentration
For 10 weight %, the amount of antioxidant 264 is 0.05g) it is terminated, 5mL ethyl alcohol is then added and is precipitated out polymer, filtering,
Washing, drying, obtain the polybutadiene P1 of 7.21g.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 7.7 ten thousand, molecular weight distributing index 3.52, is 96.5 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 13.0 weight %, branching type polybutadiene
Content be 6.7 weight %, the content of high-cis polybutadiene is 87.0 weight %.
Embodiment 2
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
Under nitrogen protection, by the hexane solution of the butadiene of the 13.79 weight % of 58g (water number is 14 μ g/g) and 6.5g
SPB-1 mixed, then be added 1.1mL Ni-Al-1 and 19.9mL BF3- 1(wherein, H2O:BF3Molar ratio is
0.22, rule 1,2- polybutadiene: the weight ratio of butadiene is 0.08, Ni: butadiene molar ratio is 1.0 × 10-4, triisobutyl
Aluminium: BF3Molar ratio be 0.28), and at 65 DEG C carry out polymerization reaction 3h, then be added antioxidant 264 ethanol solution (concentration
For 10 weight %, the amount of antioxidant 264 is 0.05g) it is terminated, 5mL ethyl alcohol is then added and is precipitated out polymer, filtering,
Washing, drying, obtain the polybutadiene P2 of 7.25g.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 7.9 ten thousand, molecular weight distributing index 3.42, is 96.2 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 14.6 weight %, branching type polybutadiene
Content be 9.4 weight %, the content of high-cis polybutadiene is 85.4 weight %.
Embodiment 3
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
Under nitrogen protection, by the hexane solution of the butadiene of the 12.43 weight % of 57.1g (water number be 10 μ g/g) and
The sPB-1 of 8.3g is mixed, and the BF of the Ni-Al-2 and 17.6mL of 1mL is then added3- 1(wherein, H2O:BF3Molar ratio is
0.21, rule 1,2- polybutadiene: the weight ratio of butadiene is 0.12, Ni: butadiene molar ratio is 0.8 × 10-4, triisobutyl
Aluminium: BF3Molar ratio be 0.30), and at 60 DEG C carry out polymerization reaction 2h, then be added antioxidant 264 ethanol solution (concentration
For 10 weight %, the amount of antioxidant 264 is 0.05g) it is terminated, 5mL ethyl alcohol is then added and is precipitated out polymer, filtering,
Washing, drying, obtain the polybutadiene P3 of 7.36g.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 10.6 ten thousand, molecular weight distributing index 3.24, is 96.8 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 24.7 weight %, branching type polybutadiene
Content be 20.0 weight %, the content of high-cis polybutadiene is 75.3 weight %.
Embodiment 4
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
According to method described in embodiment 1, the difference is that, sPB-1 is replaced using sPB-2, to obtain 7.18g polybutadiene
Alkene P4.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 7.2 ten thousand, molecular weight distributing index 3.41, is 96.1 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 15.0 weight %, branching type polybutadiene
Content be 9.9 weight %, the content of high-cis polybutadiene is 85.0 weight %.
Embodiment 5
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
Under nitrogen protection, by the hexane solution of the butadiene of the 12.74 weight % of 57.3g (water number be 15 μ g/g) and
The sPB-1 of 18.0g is mixed, and the BF of the Ni-Al-2 and 24.1mL of 1.0mL is then added3- 1(wherein, H2O:BF3Molar ratio
It is 0.27, rule 1,2- polybutadiene: the weight ratio of butadiene is 0.25, Ni: butadiene molar ratio is 0.8 × 10-4, three isobutyls
Base aluminium: BF3Molar ratio be 0.30), and at 60 DEG C carry out polymerization reaction 2h, then be added antioxidant 264 ethanol solution it is (dense
Degree is 10 weight %, and the amount of antioxidant 264 is 0.05g) it is terminated, 5mL ethyl alcohol is then added and is precipitated out polymer, mistake
Filter, washing, drying, obtain the polybutadiene P5 of 8.14g.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 8.5 ten thousand, molecular weight distributing index 3.64, is 96.0 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 25.0 weight %, branching type polybutadiene
Content be 7.0 weight %, the content of high-cis polybutadiene is 75.0 weight %.
Embodiment 6
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
In addition to butadiene hexane solution water number becomes 41 μ g/g from 22 μ g/g, other conditions are the same as embodiment 1.Wherein, H2O:
BF3Molar ratio is 0.43, and rule 1,2- polybutadiene: the weight ratio of butadiene is 0.08, Ni: butadiene molar ratio is 1.0 ×
10-4, triisobutyl aluminium: BF3Molar ratio is 0.25.To obtain 7.78g polybutadiene P6.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 8.4 ten thousand, molecular weight distributing index 3.41, is 96.4 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 9.0 weight %, branching type polybutadiene
Content is 1.0 weight %, and the content of high-cis polybutadiene is 91.0 weight %.
Embodiment 7
The present embodiment is for illustrating polybutadiene and preparation method thereof of the invention.
Except BF3Additional amount is become outside 16.4ml from 22.9ml, and other conditions are the same as embodiment 1.Wherein, H2O:BF3Molar ratio is
0.27, rule 1,2- polybutadiene: the weight ratio of butadiene is 0.08, Ni: butadiene molar ratio is 1.0 × 10-4, triisobutyl
Aluminium: BF3Molar ratio is 0.35.To obtain 8.44g polybutadiene P7.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 8.7 ten thousand, molecular weight distributing index 3.55, is 96.2 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 8.4 weight %, branching type polybutadiene
Content is 1.1 weight %, and the content of high-cis polybutadiene is 91.6 weight %.
Comparative example 1
According to method described in embodiment 1, the difference is that, BF3- 1 dosage is 14.3mL, thus H2O:BF3Molar ratio is
0.40, triisobutyl aluminium: BF3Molar ratio is 0.40；To obtain 7.37g polybutadiene DP1.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 8.9 ten thousand, molecular weight distributing index 3.50, is 96.4 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 8.7 weight %, branching type polybutadiene
Content is 0 weight %, and the content of high-cis polybutadiene is 91.3 weight %.
Comparative example 2
According to method described in embodiment 1, the difference is that, water number is adjusted to 56 μ g/g in the hexane solution of butadiene, from
And H2O:BF3Molar ratio is 0.57；To obtain 7.62g polybutadiene DP2.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 7.6 ten thousand, molecular weight distributing index 3.53, is 96.4 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 8.5 weight %, branching type polybutadiene
Content is 0 weight %, and the content of high-cis polybutadiene is 91.5 weight %.
Comparative example 3
According to method described in embodiment 1, the difference is that, the temperature of polymerization reaction is 30 DEG C；To obtain the poly- fourth of 5.16g
Diene DP3.
After the polybutadiene is extracted 72h with hexane, hexane soluble fraction (i.e. high-cis polybutadiene) is obtained through drying
Afterwards, measuring its number-average molecular weight is 9.7 ten thousand, molecular weight distributing index 3.23, is 96.8 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %.The total content that 1,2- polybutadiene and branching type polybutadiene are advised between calculating is 12.4 weight %, branching type polybutadiene
Content be 0 weight %, the content of high-cis polybutadiene is 87.6 weight %.
Test case
Stainless steel cauldron using 10L with stirring, respectively by embodiment 1, embodiment 3, embodiment 4 and comparative example 1
80 times of amplification, resulting polybutadiene and commercially available common polybutadiene rubber are (purchased from Sinopec Beijing Yanshan Mountain branch company
The BR9000 trade mark, number-average molecular weight are 7.9 ten thousand, and molecular weight distributing index 3.41 is 96.1 weights along Isosorbide-5-Nitrae-paradigmatic structure content
Measure %) respectively according to the performance of method preparation and test vulcanizate in GB/T8660-2008, test result is as shown in table 1.
Table 1
It can be seen that the polybutadiene that 1,2- polybutadiene and branching type polybutadiene are advised between not containing by the result of table 1
200% stress at definite elongation of alkene (common polybutadiene rubber) is 6.4MPa；Branching is not contained containing rule 1,2- polybutadiene
200% stress at definite elongation of the polybutadiene (comparative example 1) of type polybutadiene is 6.6MPa, that is, is improved unobvious；Contain a rule 1,2-
200% stress at definite elongation of polybutadiene and the polybutadiene (embodiment 4) containing a small amount of branching type polybutadiene is 7.2MPa, i.e.,
It is obviously improved；Polybutadiene (embodiment 1,3) containing rule 1,2- polybutadiene and containing more amount branching type polybutadiene
200% stress at definite elongation be 13.2MPa or more, i.e., significantly promoted.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of polybutadiene, which is characterized in that the polybutadiene contains: high-cis polybutadiene, branching type polybutadiene and
Between advise 1,2- polybutadiene；
Wherein, on the basis of the weight of the high-cis polybutadiene, along Isosorbide-5-Nitrae-paradigmatic structure in the high-cis polybutadiene
Content be 92 weight % or more；
The main chain of the branching type polybutadiene be high-cis paradigmatic structure and branch be between advise 1,2- paradigmatic structure；With the master
On the basis of the weight of chain, the content of suitable Isosorbide-5-Nitrae-paradigmatic structure is 92 weight % or more in the main chain；With the weight of the branch
On the basis of, the content of 1,2- paradigmatic structure is 85 weight % or more in the branch；
On the basis of weight to advise 1,2- polybutadiene between described, containing for 1,2- paradigmatic structure in 1,2- polybutadiene is advised between described
Amount is 85 weight % or more, and the crystallinity that 1,2- polybutadiene is advised between described is 10% or more.
2. polybutadiene according to claim 1, wherein on the basis of the weight of the polybutadiene, the branching type
The total content of polybutadiene and rule 1,2- polybutadiene is 5-25 weight %, and the content of the branching type polybutadiene is 1-20
Weight %, the content of the high-cis polybutadiene are 75-95 weight %；
Preferably, on the basis of the weight of the polybutadiene, the branching type polybutadiene and rule 1,2- polybutadiene
Total content is 10-25 weight %, and the content of the branching type polybutadiene is 5-20 weight %, the high-cis polybutadiene
Content is 75-90 weight %.
3. polybutadiene according to claim 1 or 2, wherein on the basis of the weight of the high-cis polybutadiene, institute
The content for stating suitable 1,4- paradigmatic structure in high-cis polybutadiene is 95 weight % or more；
Preferably, in the branching type polybutadiene, on the basis of the weight of the main chain, along Isosorbide-5-Nitrae-polymerization knot in the main chain
The content of structure is 95 weight % or more；On the basis of the weight of the branch, the content of 1,2- paradigmatic structure is in the branch
90 weight % or more；
Preferably, on the basis of the weight to advise 1,2- polybutadiene between described, 1,2- in 1,2- polybutadiene is advised between described and is polymerize
The content of structure be 90 weight % or more, advised between described 1,2- polybutadiene crystallinity be 10-40%, preferably 12-30%,
More preferably 20-30%.
4. polybutadiene described in any one of -3 according to claim 1, wherein the number of the high-cis polybutadiene is divided equally
Son amount is 50,000-150,000；
Preferably, the number-average molecular weight that 1,2- polybutadiene is advised between described is 30,000-100,000.
5. a kind of preparation method of polybutadiene, which is characterized in that this method comprises:
In organic solvent, in the presence of nickel catalyst and water, butadiene and rule 1, a 2- polybutadiene polymerize anti-
It answers, the temperature of the polymerization reaction is 50 DEG C or more；
Wherein, on the basis of the weight to advise 1,2- polybutadiene between described, 1,2- polymerization knot in 1,2- polybutadiene is advised between described
The content of structure is 85 weight % or more, and the crystallinity that 1,2- polybutadiene is advised between described is 10% or more；
The nickel catalyst contains component A, component B and component C；
Component A: carboxylic acid nickel class compound；
Component B: trialkylaluminium；
Component C: fluorochemical；
Wherein, the molar ratio of component B and component C are 0.2-0.35:1, and the molar ratio of water and component C are 0.2-0.5:1.
6. according to the method described in claim 5, wherein, the weight ratio of rule 1,2- polybutadiene and butadiene is 0.04-
0.32:1.
7. method according to claim 5 or 6, wherein described on the basis of the weight to advise 1,2- polybutadiene between described
Between advise 1,2- paradigmatic structure in 1,2- polybutadiene content be 90 weight % or more, the crystallization of 1,2- polybutadiene is advised between described
Degree is 10-40%, preferably 12-30%, more preferably 20-30%；
Preferably, the number-average molecular weight that 1,2- polybutadiene is advised between described is 30,000-100,000.
8. the method according to any one of claim 5-7, wherein the molar ratio of the component A and component B is 1:3-
10；
Preferably, the molar ratio of the component B and component C is 0.2-0.3:1；
Preferably, the molar ratio of water and component C are 0.2-0.3:1.
9. the method according to any one of claim 5-8, wherein the carboxylic acid nickel class compound be nickel naphthenate,
Caproic acid nickel, enanthic acid nickel, nickel octoate, n-nonanoic acid nickel and capric acid nickel, preferably nickel naphthenate and/or nickel octoate；
The trialkylaluminium is by formula Al (R)3Represented, R is selected from C1-C6Alkyl；Preferably, the trialkylaluminium is trimethyl
Aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, three amyl aluminium, three base aluminium and triisobutyl aluminium, preferably triisobutyl aluminium；
The fluorochemical is the one or more of hydrogen fluoride, boron trifluoride and boron trifluoride complex, preferably borontrifluoride
Diethyl etherate and/or boron trifluoride ether complex.
10. the method according to any one of claim 5-9, wherein relative to the butadiene of 1mol, the nickel system is urged
The dosage of agent makes the dosage of component A be 50-1000 μm of ol；
Preferably, it is 50-100 DEG C that the condition of the polymerization reaction, which includes: temperature, time 0.5-5h.
11. polybutadiene made from the method as described in any one of claim 5-10.
12. a kind of polybutadiene as described in any one of claim 1-4 and 11 is through vulcanizate made from vulcanization.
13. vulcanizate according to claim 12, wherein 200% stress at definite elongation of the vulcanizate is 7.2MPa or more.
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| CN111848849A (en) * | 2020-07-01 | 2020-10-30 | 浙江传化合成材料有限公司 | Continuous preparation process of nickel-based butadiene rubber and rare earth-based butadiene rubber |
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| CN105837873A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Mixed rubber, preparation method and application thereof |
| JP2017132958A (en) * | 2016-01-29 | 2017-08-03 | 株式会社ブリヂストン | Rubber composition and tire |
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| JPS5477653A (en) * | 1977-12-02 | 1979-06-21 | Bridgestone Corp | Compounded rubber composition for sidwwall |
| US4255296A (en) * | 1977-12-02 | 1981-03-10 | Bridgestone Tire Company Limited | Polybutadiene rubber composition |
| CN104231119A (en) * | 2013-06-24 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of long-chain branched cis-rich polybutadiene |
| CN105837873A (en) * | 2015-01-15 | 2016-08-10 | 中国石油天然气股份有限公司 | Mixed rubber, preparation method and application thereof |
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| CN111848849B (en) * | 2020-07-01 | 2021-02-19 | 浙江传化合成材料有限公司 | Continuous preparation process of nickel-based butadiene rubber and rare earth-based butadiene rubber |
| EP3932958A1 (en) * | 2020-07-01 | 2022-01-05 | Zhejiang Transfar Synthetic Material Co., Ltd. | Method for continuously preparing nickel catalysed cis-polybutadiene and rare earth catalysed cis-polybutadiene |
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