CN104098726A - Polybutadiene rubber and preparation method thereof - Google Patents
Polybutadiene rubber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polybutadiene rubber and a preparation method thereof. The polybutadiene rubber comprises 5-15wt% of a structural unit obtained by 1,2-polymerization of 1,3-butadiene and 85-95wt% of a structural unit obtained by 1,4-polymerization of 1,3-butadiene. The polybutadiene rubber has cis-1,4-structural unit content of 30-45wt%, a number-average molecular weight of 40000-500000 and molecular weight distribution of 2.0-3.0. The polybutadiene rubber obtained by the preparation method has wide molecular weight distribution, guarantees complete monomer conversion in reasonable staying time and has gelling controllability in the reaction.
Description
Technical field
The present invention relates to a kind of polybutadiene rubber and preparation method thereof.
Background technology
Adopting lithium is that polybutadiene rubber (LCBR) prepared by polymerization technique is not only PS and the impact-resistant modified first-selected glue kind of ABS resin, is also the ideal glue of tire or rubber overshoes manufacture simultaneously.Because it has excellent processing characteristics, high fillibility, wear resistance, dimensional stability, low hysteresis loss, low tension set, in tire production, LCBR, except with other glue kinds and be used as tread rubber uses, is also more widely used in radial bead adhesive and triangle rubber.
As tire glue, LCBR need to be used with the reinforcing filler such as silicon-dioxide, carbon black and vulcanizing agent, promotor and other additive blend, these additives are absorbed and are dispersed in subsequently speed and the efficiency in rubber matrix, be the processing characteristics of rubber, depend on more molecular weight distribution coefficient (Mw/Mn) size of rubber.Generally speaking, the narrow molecular weight distribution of polymkeric substance, poor processability, suitably its molecular weight distribution of broadening, can improve its processing characteristics.Practice prepared by theoretical investigation and tire shows, the polymkeric substance of Mw/Mn < 1.3 is difficult to mix with filler conventionally, and the polymkeric substance of Mw/Mn between 1.8 to 2.5 has good processing characteristics.If the Mw/Mn of polymkeric substance is greater than 2.5, the deployment conditions of filler in polymeric matrix is by variation.Therefore,, as tire glue, LCBR must have suitable Mw/Mn.
LCBR synthesis technique has batchwise polymerization technique and continuous polymerization technique.The narrow molecular weight distribution of the LCBR that batch technology is synthetic, not only more difficult processing, simultaneously sizing material easy-cold flow.The molecular weight distribution of the LCBR that continuous processing is synthetic is with wider.When carrying out living polymerization in tank reactor intermittence, the residence time of all molecules in reactor is identical, because rate of initiation reaction is far above reaction of propagation speed, in the situation that there is not chain termination and chain transfer reaction in system, synthesized polymkeric substance is identical aspect molecular weight, and the Mw/Mn that generates polymkeric substance equals 1.Therefore, the broadening batchwise polymerization technique of should taking measures is prepared the Mw/Mn of polymkeric substance, to improve processing characteristics and the anti-cold flow properties of rubber.Under batchwise polymerization technique, conventionally adopt the modes such as chelate initiator, substep initiation, coupling to carry out the molecular weight distribution of broadening polymkeric substance, but complex technical process.
While carrying out living polymerization in continuous tank reactor, molecule in reactor has the different residence time, its molecular weight there are differences, in the situation that not there is not chain termination and chain transfer reaction, the Mw/Mn that continuous processing is prepared polymkeric substance, except outside the Pass the residence time with material has, also depends on the transformation efficiency that total reactor number and monomer reach in each reactor.In theory, in single complete stirred-tank reactor type reactor (CSTR), the Mw/Mn of outlet polymkeric substance equals 2, and with the increase of number of reactors, the Mw/Mn of outlet polymkeric substance reduces gradually.Compare batchwise polymerization technique, adopt the LCBR of the synthetic Mw/Mn of continuous polymerization technique between 1.8 to 2.5 easier.
US20070219316A1 discloses a kind of method of carrying out continuous production statistics vinyl-arene/conjugated diolefine random copolymers under at least two tandem reactors exist.The method is in hydrocarbon solvent, at the temperature of 30-120 ℃, under the existence of at least one initiator and 2-methoxy ethyl tetrahydrofuran (THF) (THFA-ethyl) properties-correcting agent, by waiting temperature control, obtaining weight-average molecular weight is 200,000 to 800,000, Mw/Mn is statistics vinyl-arene/conjugated diolefine random copolymers of 1.6 to 2.5.Though the Mw/Mn of the method synthesized polymkeric substance meets the demands, the increase of polymkeric substance Mw/Mn is to realize by chain transfer or chain termination reaction between properties-correcting agent in reaction process and spike.Owing to existing the chain between properties-correcting agent and spike to shift or chain termination reaction in the method reaction process, make the monomer conversion of system not high.And the method does not add gel inhibitor.Continuous polymerization technique due to the back-mixing of material and a part of swelling macromole be deposited on reactor wall, stir on wall, heat transfer wall, make " activity " macromole prolonged stay in reactor, these " activity " macromole constantly contact with the monomer adding continuously, molecular chain increases thereupon and then forms insoluble super large molecule, i.e. gel.Do not add gel inhibitor, be difficult to the long-term operation of assurance device.But, add gel inhibitor, due to gel inhibitor can with system in super large molecule generation chain transfer reaction, and then suppress the generation of gel, therefore, adding of gel inhibitor, also can have a negative impact to system monomer conversion simultaneously.
US5891947 discloses a kind of method that adopts two still series connection isothermal process to prepare segmented copolymer, after the method is distributed initiator, solvent, styrene monomer, butadiene type monomer, conditioning agent, irregular agent according to a certain percentage, add continuously respectively in two polymeric kettles, at the temperature of 0-154 ℃, the molecular weight distributing index of synthesized polymkeric substance (Mw/Mn) can reach 2.28-3.68 left and right.Sectional feeding technique is higher to the specification of quality of raw material, and technology controlling and process relative complex, in the situation that single still residence time of material is identical with polymeric kettle quantity, is limit by monomer conversion, compare material all by first still charging, sectional feeding technique cannot be prepared the polymkeric substance that base molecule amount is higher.And this invention does not adopt gel inhibitor, be difficult to the long-term operation of assurance device.
Summary of the invention
The object of the invention is when overcoming in prior art continuous polymerization technique synthesizing polybutadiene rubber, for obtaining wide molecular weight distribution, need by increase initiator add-on or by the shortcoming of sectional feeding, provide a kind of within the rational residence time, guarantee system monomer transforms completely, and can prepare the preparation method of wide molecular weight distribution polybutadiene rubber.
The invention provides a kind of polybutadiene rubber, wherein, the weight of described polybutadiene rubber of take is benchmark, the content of the structural unit that 1,3-butadiene forms with 1,2-polymerization methods is 5-15 % by weight, with 1, the content of the structural unit that 4-polymerization methods forms is 85-95 % by weight, and the content of the cis-Isosorbide-5-Nitrae-structural unit of described polybutadiene rubber is 30-45 % by weight, number-average molecular weight is 40,000-500,000, molecular weight distribution is 2-3.
The present invention also provides a kind of preparation method of polybutadiene rubber, the method comprises and will contain 1, the reaction mass of 3-divinyl, organic lithium initiator, inert solvent, gel inhibitor is sent into the reactor of n series connection continuously, wherein, in first to n-1 reactor, temperature of reaction is 70-110 ℃, and reaction pressure is that 0.6-1.0MPa, the residence time are 20-60 minute, the temperature of reaction of n reactor is than the high 20-50 ℃ of the temperature of reaction of the first reactor, n >=2.
The synthetic polybutadiene rubber obtaining of method of the present invention, molecular weight distribution is wide, can guarantee that conversion of monomer is complete within the rational residence time simultaneously, and in reaction process, gel is controlled.
Embodiment
The invention provides a kind of polybutadiene rubber, wherein, the weight of described polybutadiene rubber of take is benchmark, the content of the structural unit that 1,3-butadiene forms with 1,2-polymerization methods is 5-15 % by weight, with 1, the content of the structural unit that 4-polymerization methods forms is 85-95 % by weight, and the content of the cis-Isosorbide-5-Nitrae-structural unit of described polybutadiene rubber is 30-45 % by weight, number-average molecular weight is 40,000-500,000, molecular weight distribution is 2-3.
In the present invention, term " basic glue " refers to the butadiene polymer of gained after solution polymerization, and therefore, in the present invention, " butadiene polymer " can be interchangeable with " basic glue "." residence time " refers to the residence time of the reaction mass in single reactor, in the present invention, and the polymerization time=mono-still residence time * still number.
According to the present invention, preferably, the weight of described polybutadiene rubber of take is benchmark, the content of the structural unit that 1,3-butadiene forms with 1,2-polymerization methods is 8-13 % by weight, with 1, the content of the structural unit that 4-polymerization methods forms is 87-92 % by weight, and the content of the cis-Isosorbide-5-Nitrae-structural unit of described polybutadiene rubber is 35-40 % by weight, number-average molecular weight is 50,000-400,000, molecular weight distribution is 2.2-2.8.
The preparation method of polybutadiene rubber according to a second aspect of the invention, the method comprises and will contain 1, the reaction mass of 3-divinyl, organic lithium initiator, inert solvent, gel inhibitor is sent into the reactor of n series connection continuously, wherein, in first to n-1 reactor, temperature of reaction is 70-110 ℃, and reaction pressure is that 0.6-1.0MPa, the residence time are 20-60 minute, the temperature of reaction of n reactor is than the high 20-50 ℃ of the temperature of reaction of the first reactor, n >=2.Preferably, in first to n-1 reactor, temperature of reaction is 80-100 ℃, and reaction pressure is that 0.7-0.8MPa, the residence time are 20-40 minute; The temperature of reaction of n reactor is than the high 20-40 ℃ of the temperature of reaction of the first reactor.More preferably, first is identical to the temperature of reaction of n-1 reactor, and the temperature of reaction of each still is 80-100 ℃; The temperature of reaction of n reactor is 120-140 ℃.According to the present invention, those skilled in the art can know, and temperature of reaction is identical to be referred to that temperature in reaction process differs and be less than or equal to 2 ℃.
Method of the present invention, although the present invention does not have special requirement for the number of reactor, can carry out suitable selection according to transformation efficiency and the residence time of reaction, but consider from reaction efficiency and reaction cost, preferably, n is any one integer in 2-6, and more preferably any one integer in 2-4, is further preferably 2 or 3.
According to the present invention, described gel inhibitor can, for the conventional various gel inhibitors in this area, be not particularly limited.Preferably, described gel inhibitor can be selected from least one in 1，2-butadiene, tertiary pentyloxy potassium, silicon tetrachloride, Tetramethyl Ethylene Diamine and tetrahydrofuran (THF), is preferably 1，2-butadiene.
The present invention is not particularly limited for the content of described gel inhibitor, can select for the routine of this area.Preferably, with the 1,3-butadiene of 1,000g, for benchmark, the consumption 0.08-0.25g of described gel inhibitor, is preferably 0.1-0.15g.
According to the present invention, the various organic lithium initiators that can cause anionoid polymerization that described organic lithium initiator can be known to the skilled person, for example, described organic lithium initiator can be that molecular formula is the organic lithium initiator of RLi, wherein, R is straight or branched alkyl, cycloalkyl or aryl; Particularly, described organic lithium initiator can be selected from one or more in lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium, is preferably n-Butyl Lithium and/or s-butyl lithium.
The present invention is not particularly limited the content of described organic lithium initiator, can select according to actual needs suitable add-on.Those skilled in the art should hold intelligible, in the time need to preparing the larger polybutadiene rubber of molecular weight, can reduce the consumption of organic lithium initiator, and now rate of polymerization also can correspondingly reduce; In the time need to preparing the polybutadiene rubber of molecular weight, can increase the consumption of organic lithium initiator, now rate of polymerization also can correspondingly increase.Therefore, consider rate of polymerization and the molecular size range of the polybutadiene rubber that obtains, under preferable case, the 100 grams of institute's 1,3-butadienes of take are benchmark, and the consumption of described organic lithium initiator is 0.2-2.5mmol.
According to the present invention, described organic solvent can be existing various organic solvents of not having an effect with reactant and resultant, and for example, described organic solvent can be selected from organic hydrocarbon solvent, is preferably C
3-C
12organic hydrocarbon solvent; Particularly, described organic solvent can be selected from propane, butane, pentane, normal hexane, heptane, octane, decane, pentamethylene, methylcyclopentane, hexanaphthene, suberane, cyclooctane and raffinate oil in one or more.Described raffinating oil refers in petroleum refining process, is rich in catalytic reforming gasoline remaining distillate after extraction aromatic hydrocarbons of aromatic hydrocarbons, and its main component is C
6-C
8alkane and naphthenic hydrocarbon.Preferably, described organic solvent be selected from pentane, normal hexane, hexanaphthene and raffinate oil in one or more; More preferably, described organic solvent is the mixed solvent of normal hexane and hexanaphthene, and wherein, the gross weight of described normal hexane and hexanaphthene of take is benchmark, and the content of described normal hexane can be 5-30 % by weight.The consumption of described organic solvent is the conventional amount used of anionic polymerisation, and usually, it is 10-30 % by weight that the consumption of described organic solvent makes the concentration of monovinylarene and conjugated diene.
As a rule, anionic polymerisation system does not have obvious termination reaction and shift reaction, and after ruing out of whole monomers, active centre still exists.Therefore,, after polyreaction completes, the copolymer solution obtaining should be contacted with terminator so that active centre inactivation.The consumption of described terminator can be selected according to added organic lithium initiator, and as a rule, the mol ratio of the consumption of described terminator and the consumption of organic lithium initiator can be 0.1-1:1.Described terminator can be the existing various terminators that can make anion active center inactivation, for example, can be selected from one or more in water, methyl alcohol, ethanol and Virahol, is preferably Virahol.
According to the present invention, airborne water vapour can react by termination of anionic polymerization, and therefore, in order to be more conducive to the carrying out of polyreaction, described polyreaction should preferably be carried out in inert atmosphere.Described inert atmosphere refers to not with reactant and produces any one gas or the gaseous mixture of thing generation chemical reaction, as one or more in nitrogen and periodic table of elements zero group gas.Keep inert atmosphere method can in reaction system, pass into above-mentioned not with any one gas or the gaseous mixture of reactant and resultant generation chemical reaction.
The preparation method of polybutadiene rubber of the present invention after being also included in copolymer solution being contacted with terminator removes organic solvent.The method that removes described organic solvent is known to the skilled person, and this is no longer going to repeat them.In order to obtain the polybutadiene rubber that ageing-resistant performance is more excellent, preferably, the preparation method of described polybutadiene rubber also comprise copolymer solution is contacted with terminator after, remove before organic solvent, described copolymer solution is contacted with anti-aging agent.The consumption of described anti-aging agent can be the 0.1-2 % by weight of polybutadiene rubber content conventionally.Described anti-aging agent can for existing various can be as the anti-aging agent of polybutadiene rubber additive, for example, described anti-aging agent can be phenols and/or amines antioxidants, be preferably selected from 2,6-ditertbutylparacresol (abbreviation antioxidant 264), tert-butyl catechol and 2, one or more in 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (abbreviation antioxidant 2246).
In the method for the invention, polymkeric substance glue can, by similar fashion Precipitations from solvent such as alcoholization precipitation, centrifugation, filtration, decant, water vapour cohesions, also can adopt stripping mode that the volatile organic solvent in polymkeric substance is separated.
By embodiment and comparative example, describe the present invention in detail below, but scope of the present invention is not limited to these embodiment.
In present specification, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
In the following examples and comparative example, various performances are evaluated by the following method:
(1) the molecular weight and molecular weight distribution coefficients by using of the polymkeric substance Japan Shimadzu LC-10A of company series gel permeation chromatograph, measures at normal temperatures, and mobile phase solvent is THF.
(2) microtexture (, 1,3-divinyl is with 1,2-polymerization methods and 3, the amount of the amount of the structural unit of 4-polymerization methods formation, the structural unit forming with Isosorbide-5-Nitrae-polymerization methods) adopt the Switzerland AVANCE DRX400MHz of Bruker company nuclear-magnetism wave of oscillation spectrometer, normal temperature is measured, liquid pool method, solvent is CS2, wherein, and 1,4-Bd% represents that divinyl is with 1, the content of the structural unit that the mode of 4-polymerization forms, 1,2-Bd% represents that divinyl is with 1, the content of the structural unit that the mode of 2-polymerization forms.
(3) solvent composition and monomer reaction transformation efficiency adopt Shimadzu GC-14A flame gas chromatograph to measure, and marker method is calculated.
(4) mensuration of gel content adopts and dissolves the filtration method mensuration of weighing, this testing method is: accurately weigh 10 grams, dried sample glue, according to 5% weight of toluene solution, be configured, after sample glue dissolves completely, through 360 order stainless (steel) wire suction filtration post-dryings, weigh, record the gel content in sample.
(5) mooney viscosity (ML) adopts Japanese SHIMADZU SMV-300 tester, and by GB/T1232.1-2,000 measures.
(6) dissipation factor in dynamic properties adopts the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure, frequency 2Hz, 5 ℃/min of temperature rise rate ,-120 ℃ to 100 ℃, sample size 40mm * 5mm * 1mm.
In the present invention, transformation efficiency calculation formula is as follows:
Embodiment and comparative example are all to carry out in 5 liters of polymerization reaction kettles of many still series connection, adopt the feeding manner of bottom in and top out, carry out full still operation.Solvent, monomer and other reaction promoter be in advance through adding at the bottom of the still still of confessing one's crime after mixing, and initiator is confessed one's crime separately at the bottom of still still and added after solvent cut.Reaction mass is after first still stays for some time, at the bottom of first still still top overflow to the second still still; The second still reaction mass enters at the bottom of the 3rd still still, from the 3rd still still top overflow, goes out, and the rest may be inferred.Residence time variation changes to realize by mass flow.Each temperature of reaction kettle is controlled by thermal medium in chuck and exothermic heat of reaction Comprehensive Control, the charging of raw material normal temperature.
Embodiment 1
This embodiment is for illustrating the preparation method of polybutadiene rubber provided by the invention.
Reaction is carried out in 25 liters of polymerization reaction kettles that are connected in series.Under high pure nitrogen protective atmosphere, single still residence time of material is 30 minutes, and polymeric kettle internal pressure is controlled at 0.7MPa(gauge pressure).The input speed of various reaction masses is: mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) 6199g/h, 1,3-butadiene 1361g/h, n-Butyl Lithium 1.09g/h and 1，2-butadiene 0.68g/h.Controlling first still polymeric reaction temperature is 100 ± 2 ℃, the second still polymeric reaction temperature is 125 ± 2 ℃, the second still outlet adds terminator Virahol 1.02g/h termination reaction, and adds the anti-aging agent Irganox1520 of monomer weight 0.2%, obtains polybutadiene rubber glue.Then glue is carried out to the processing of devaporation desolventizing.Molecular parameter, the gel content of conversion of monomer situation and polybutadiene rubber are as shown in table 1.
Embodiment 2
This embodiment is for illustrating the preparation method who the invention provides polybutadiene rubber.
Adopt the experiment condition identical with embodiment 1, unique difference is that the add-on of 1，2-butadiene is 0.41g/h.Molecular parameter, the gel content of conversion of monomer situation and polybutadiene rubber are as shown in table 1.
Embodiment 3
This embodiment is for illustrating the preparation method who the invention provides polybutadiene rubber.
Adopt the experiment condition identical with embodiment 1, difference is that the add-on of n-Butyl Lithium is 0.725g/h, and quantity of isopropanol is 1.02g/h.Molecular parameter, the gel content of conversion of monomer situation and polybutadiene rubber are as shown in table 1.
Comparative example 1
Adopt the experiment condition identical with embodiment 1, unique difference is that the second still temperature becomes 100 ± 2 ℃ from 125 ± 2 ℃.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 1.
Table 1
| Sequence number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| First still monomer conversion, % | 99.5 | 99.7 | 99.2 | 99.2 |
| The second still monomer conversion, % | 100 | 100 | 99.9 | 100 |
| First still Mn, ten thousand | 7.9 | 8.0 | 11.9 | 8.0 |
| First still Mw/Mn | 1.89 | 1.90 | 1.91 | 1.90 |
| The second still Mn, ten thousand | 8.1 | 8.2 | 12.1 | 8.1 |
| The second still Mw/Mn | 2.41 | 2.62 | 2.24 | 1.78 |
| Contents of ethylene, % by weight | 12.1 | 12.4 | 12.3 | 12.5 |
| Gel content, ppm | 80 | 120 | 70 | 70 |
Note: Mn is number-average molecular weight; Mw is weight-average molecular weight; Mw/Mn is molecular weight distribution; Contents of ethylene is that the structural unit that 1,3-butadiene forms with 1,2-polymerization methods accounts for the percentage composition that 1,3-butadiene polymerization forms total structural unit.
As seen from the data in Table 1, embodiment 1 and comparative example 1 relatively, adopt alternating temperature technique, for improving polymkeric substance Mw/Mn successful.Embodiment 1 and embodiment 2 are more known, change 1，2-butadiene consumption obvious on monomer conversion and polymkeric substance Mw/Mn impact, reduce 1，2-butadiene consumption, and monomer conversion remains unchanged substantially, and the Mw/Mn of polymkeric substance increases.
Embodiment 4
This embodiment is for illustrating the preparation method who the invention provides polybutadiene rubber.
Reaction is carried out in 35 liters of polymerization reaction kettles that are connected in series.Under high pure nitrogen protective atmosphere, single still residence time of material is 20 minutes, and polymeric kettle internal pressure is controlled at 0.7MPa(gauge pressure).The input speed of various reaction masses is: mixed solvent (hexanaphthene and normal hexane, weight ratio is 88:12) 9525g/h, divinyl 1814g/h, n-Butyl Lithium 0.58g/h and 1，2-butadiene 0.91g/h.Controlling first still polymeric reaction temperature is 90 ± 2 ℃, the second still polymeric reaction temperature is 90 ± 2 ℃, the 3rd still polymeric reaction temperature is 135 ± 2 ℃, end still (i.e. the 3rd still) outlet adds terminator Virahol 0.54g/h termination reaction, and add the anti-aging agent Irganox1520 of monomer weight 0.2%, obtain polybutadiene rubber glue, then glue is carried out to the processing of devaporation desolventizing.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 2.
Embodiment 5
Adopt the experiment condition identical with embodiment 4, unique difference is that normal-butyl add-on is 0.38g/h, and quantity of isopropanol is 0.36g/h.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 2.
Embodiment 6
Adopt the experiment condition identical with embodiment 4, unique difference is that normal-butyl add-on is 0.29g/h, and quantity of isopropanol is 0., 27g/h.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 2.
Embodiment 7
Adopt the experiment condition identical with embodiment 4, unique difference is that the 3rd still temperature becomes 150 ± 2 ℃ from 130 ± 2 ℃.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 2.
Comparative example 2
Adopt the experiment condition identical with embodiment 4, unique difference is that the 3rd still temperature becomes 90 ± 2 ℃ from 130 ± 2 ℃.The performance of conversion of monomer situation and polybutadiene rubber is as shown in table 2.
Table 2
| Sequence number | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 2 |
| First still monomer conversion, % | 86.6 | 84.2 | 81.3 | 86.1 | 87.1 |
| The second still monomer conversion, % | 99.7 | 98.1 | 97.8 | 99.2 | 99.4 |
| The 3rd still monomer conversion, % | 100 | 100 | 99.9 | 100 | 100 |
| First still Mw/Mn | 1.91 | 1.90 | 1.89 | 1.92 | 1.92 |
| The second still Mw/Mn | 1.84 | 1.80 | 1.82 | 1.91 | 1.83 |
| The 3rd still Mn, ten thousand | 20.5 | 30.7 | 40.0 | 20.6 | 19.8 |
| The 3rd still Mw/Mn | 2.33 | 2.31 | 2.35 | 2.62 | 1.65 |
| Contents of ethylene, % by weight | 12.5 | 12.1 | 12.2 | 12.4 | 12.0 |
| Gel content, ppm | 36 | 41 | 37 | 35 | 38 |
Note: Mn is number-average molecular weight; Mw is weight-average molecular weight; Mw/Mn is molecular weight distribution; Contents of ethylene is that 1,3-butadiene accounts for the percentage composition of total structural unit of 1,3-butadiene polymerization formation with the structural unit of 1,2-polymerization methods formation.
As seen from the data in Table 2, the data of comparative example 4,5 and embodiment 6 are visible, and along with the reduction of butyllithium add-on, first still monomer conversion obviously reduces, and therefore increase by 1 reactor with bonding transformation rate.Comparative example 4 is visible with the data of embodiment 7, improves last still polymeric reaction temperature, and polymkeric substance Mw/Mn obviously increases.
Claims (10)
1. a polybutadiene rubber, is characterized in that, the weight of described polybutadiene rubber of take is benchmark, the content of the structural unit that 1,3-butadiene forms with 1,2-polymerization methods is 5-15 % by weight, with 1, the content of the structural unit that 4-polymerization methods forms is 85-95 % by weight, and the content of the cis Isosorbide-5-Nitrae-structural unit of described polybutadiene rubber is 30-45 % by weight, number-average molecular weight is 40,000-500,000, molecular weight distribution is 2-3.
2. polybutadiene rubber according to claim 1, wherein, the weight of described polybutadiene rubber of take is benchmark, the content of the structural unit that 1,3-butadiene forms with 1,2-polymerization methods is 8-13 % by weight, with 1, the content of the structural unit that 4-polymerization methods forms is 87-92 % by weight, and the content of the cis Isosorbide-5-Nitrae-structural unit of described polybutadiene rubber is 35-40 % by weight, number-average molecular weight is 50,000-400,000, molecular weight distribution is 2.2-2.8.
3. the preparation method of a polybutadiene rubber, the method comprises and will contain 1, the reaction mass of 3-divinyl, organic lithium initiator, inert solvent, gel inhibitor is sent into the reactor of n series connection continuously, wherein, in first to n-1 reactor, temperature of reaction is 70-110 ℃, and reaction pressure is that 0.6-1MPa, the residence time are 20-60 minute, the temperature of reaction of n reactor is than the high 20-50 ℃ of the temperature of reaction of the first reactor, n >=2.
4. method according to claim 3, wherein, in first to n-1 reactor, temperature of reaction is 80-100 ℃, reaction pressure is that 0.7-0.8MPa, the residence time are 20-40 minute; The temperature of reaction of n reactor is than the high 20-40 ℃ of the temperature of reaction of the first reactor.
5. according to the method described in claim 3 or 4, wherein, first is identical to the temperature of reaction of n-1 reactor, and the temperature of reaction of each still is 80-100 ℃; The temperature of reaction of n reactor is 120-140 ℃.
6. method according to claim 3, wherein, n is any one integer in 2-6, is preferably any one integer in 2-4, most preferably is 2 or 3.
7. method according to claim 3, wherein, described gel inhibitor is selected from least one in 1，2-butadiene, tertiary pentyloxy potassium, silicon tetrachloride, Tetramethyl Ethylene Diamine and tetrahydrofuran (THF), is preferably 1，2-butadiene.
8. according to the method described in claim 3 or 6, wherein, with the weight of the 1,3-butadiene of 1,000g, for benchmark, the consumption of described gel inhibitor is 0.08-0.25g, and preferable amount is 0.1-0.15g.
9. method according to claim 3, wherein, the described polymerization single polymerization monomer a of 100g of take is benchmark, the consumption of described organic lithium initiator is 0.2-2.5mmol.
10. the polybutadiene rubber that in claim 3-9, described in any one prepared by method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104311762A (en) * | 2014-11-19 | 2015-01-28 | 中国科学院长春应用化学研究所 | Random-syndiotactic block polybutadiene and preparation method thereof |
| CN104558328A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Polybutadiene rubber, preparation method of polybutadiene rubber and oil-extended rubber |
| CN107337754A (en) * | 2016-05-03 | 2017-11-10 | 中国石油化工股份有限公司 | Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene |
| CN114395062A (en) * | 2022-01-20 | 2022-04-26 | 黎明化工研究设计院有限责任公司 | Preparation method of liquid polybutadiene with wide molecular weight distribution |
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| CN101280034A (en) * | 2008-05-23 | 2008-10-08 | 北京化工大学 | Vinyl content method for controlling polybutadiene in elastomer |
| CN102115509A (en) * | 2010-12-31 | 2011-07-06 | 大连理工大学 | Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof |
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| CN101280034A (en) * | 2008-05-23 | 2008-10-08 | 北京化工大学 | Vinyl content method for controlling polybutadiene in elastomer |
| CN102115509A (en) * | 2010-12-31 | 2011-07-06 | 大连理工大学 | Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104558328A (en) * | 2013-10-17 | 2015-04-29 | 中国石油化工股份有限公司 | Polybutadiene rubber, preparation method of polybutadiene rubber and oil-extended rubber |
| CN104311762A (en) * | 2014-11-19 | 2015-01-28 | 中国科学院长春应用化学研究所 | Random-syndiotactic block polybutadiene and preparation method thereof |
| CN107337754A (en) * | 2016-05-03 | 2017-11-10 | 中国石油化工股份有限公司 | Conjugated diene polymer and preparation method thereof and polybutadiene and polyisoprene |
| CN114395062A (en) * | 2022-01-20 | 2022-04-26 | 黎明化工研究设计院有限责任公司 | Preparation method of liquid polybutadiene with wide molecular weight distribution |
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| CN104098726B (en) | 2016-09-21 |
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