CN1062276C - Conjugate diolefin and mono-vinyl arene two-block copolymer and its synthesis method - Google Patents
Conjugate diolefin and mono-vinyl arene two-block copolymer and its synthesis method Download PDFInfo
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Abstract
The present invention relates to a diblock copolymer of conjugated diolefin and monovinyl arene, and a synthetizing method thereof. In the method, a polychelated organolithium compound is used as an initiating agent, one-step addition of an inert solvent, a monomer and the initiating agent and two-step addition of a structure conditioning agent are adopted to prepare the diblock copolymer by controlling conversion rate, wherein the polychelated organolithium compound as the initiating agent is prepared from divinyl benzene and organic monolithium subjected to a reaction in a hydrocarbon solvent. The method is characterized in that the branched copolymer having the advantages of wide molecular weight distribution, high mooney viscosity, high wet slip resistance and low rolling resistance can be obtained without coupling, and the copolymer is especially suitable for tyre tread manufacture.
Description
The present invention relates to a kind of conjugated diolefine and monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and synthetic method thereof, more particularly, relating to a kind of is the method for synthetic high wet-sliding resistant of initiator and low-rolling-resistance Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock with the multi-chelate organolithium compound.
The current rubber of tread rubber of automobile tires that is applicable to not only will have good tensile and wear resisting property, also will have high wet-sliding resistant and low-rolling-resistance, could satisfy demand energy-conservation and safety traffic like this.And these two kinds of performance demands of low-rolling-resistance and high wet-sliding resistant are conflicting, and the rubber of single variety is difficult to satisfy simultaneously this two kinds of requirements.Method with blend just makes two kinds of performances improve to some extent two kinds of blend rubbers that have low-rolling-resistance and high wet-sliding resistant respectively, is difficult to obtain the ideal product.For example, the butylbenzene copolymer that contains 10～30%wt. bonding vinylbenzene and the conjugated diolefine that is no more than the 20%wt vinyl has relative high anti-slippery, contain the polybutadiene rubber that is no more than 20% vinyl and have low rolling resistance and high wear resistance, the mixture of the two has been used to make doughnut, yet other characteristic of this mixture particularly anti-slippery can not be satisfactory.
Recently, for improving the anti-slippery and the rolling resistance of rubber item, attempt mainly to reach with divinyl rubber or the styrene-butadiene rubber(SBR) that organic lithium initiator obtains by modification.For example, method with anionoid polymerization can synthesize a kind of AB Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock with different styrene contents and contents of ethylene, can make the multipolymer of gained have high wet-sliding resistant and low-rolling-resistance simultaneously by the content of adjusting vinylbenzene, vinyl in two sections ratios shared in whole multipolymer of A, B in the copolymer rubber molecule and two sections.The rolling resistance of rubber item and anti-slippery can be characterized by 50 ℃ of tan δ values with-10 ℃ in its viscoelastic spectra usually, and 50 ℃ tan δ value is low more, and the rolling resistance of rubber is more little, and-10 ℃ tan δ value is high, and the anti-slippery of rubber is good more.
U.S. Pat 4463133 discloses a kind of diblock styrene-butadiene rubber(SBR) composition, wherein contains A, the B Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of 20%wt. at least, comprises the multipolymer of containing metal-carbon bond of 20%wt. in the molecular chain of this segmented copolymer at least; The open EP0270927 of European patent discloses a kind of rubber combination that is used for tire tread, said composition comprises a kind of rubber components of block copolymer containing, this segmented copolymer is a kind of A that contains in fact, the branched block multipolymer of B diblock, 40%wt. is coupling agent modified with trifunctional or four-functional group at least in the whole molecular chain of this segmented copolymer, the said composition tool is the diblock butylbenzene copolymer that high wet-sliding resistant and low-rolling-resistance are arranged, said composition has high wet-sliding resistant and low-rolling-resistance, the preparation method of this segmented copolymer is to be that initiator carries out the A section in the presence of polar compound or the B section is synthetic with the organic single-lithium, it is synthetic to carry out next section then, carry out linked reaction with coupling agent again, use the terminator termination reaction at last.Their shortcoming is to carry out modification to multipolymer with coupling agent, just can obtain multipolymer branching, that molecular weight distribution is wide, that performance is good.
U.S. Pat 4433109 discloses a kind of segmented copolymer of styrene butadiene, it comprises the random copolymerization section and the selectable polyhutadiene section of the styrene butadiene of two sections different contents of ethylene and bonding styrene content, and this multipolymer has high wet-sliding resistant and low-rolling-resistance.Its shortcoming is that products obtained therefrom is that line style, narrow molecular weight distribution, mooney viscosity are low, and the tear strength of product is low, the poor processability of product; The open EP054440 of European patent improves on this basis, by the segmented copolymer with the above-mentioned gained of coupling agent coupling the processing characteristics of product and tearing toughness is improved.Its shortcoming also just is being this: promptly must carry out modification to multipolymer with coupling agent, just can obtain multipolymer branching, that molecular weight distribution is wide, that performance is good.
The object of the present invention is to provide a kind of easy synthesis of conjugate diene and the method for monovinylarene diblock branched copolymers, promptly can obtain multipolymer branching, wide molecular weight distribution, high Mooney, that performance is good without coupling.
Another object of the present invention is to use multi-chelate organolithium is synthetic conjugated diolefine and the monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock with high wet-sliding resistant and low-rolling-resistance of initiator.
To achieve the above object of the invention, the technical solution used in the present invention is: inert solvent, conjugated diene, monovinylarene, the structure regulator that will react required once add, add multi-chelate organolithium initiator then, it is synthetic to carry out the A section in the presence of initiator, makes polymerisation conversion reach 10～90%; Add structure regulator, carry out the B section and synthesize; After polyreaction finishes, add terminator and anti-aging agent, and condense, thereby make conjugated diolefine and monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.
The present invention relates to a kind of synthesis of conjugate diene and monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and preparation method thereof.The preparation method comprises:
(1) adds inert solvent, conjugated diene, monovinylarene, structure regulator, add multi-chelate organolithium initiator then, in the presence of initiator, carry out the A section and synthesize, make polymerisation conversion reach 10～90%, be 20～50% preferably, best is 30%;
(2) add structure regulator, carry out the B section and synthesize;
(3) after polyreaction finishes, add terminator and anti-aging agent, and condense.
Wherein A section and B section are the random copolymerization section of conjugated diolefine and monovinylarene, just these two kinds monomeric content differences in these two sections;
Wherein multi-chelate organolithium initiator is to be reacted in varsol by Vinylstyrene (DVB) and organic single-lithium to make.
Single step reaction in varsol obtains multi-chelate organolithium initiator of the present invention by DVB and organic single-lithium, the organic pair of lithium and the organic many lithiums that wherein have organic single-lithium and generate with the Vinylstyrene reaction.In reaction process, can add conjugated diolefine or mono vinyl arenes monomer as additive,,, obtain the homogeneous phase initiator solution to improve initiator solubleness in hydrocarbon solution so that on two lithiums and multi-lithium initiator molecule, form the polymkeric substance galianconism.
The used DVB of the present invention can be 1,3-Vinylstyrene, 1, and 4-Vinylstyrene or their mixture, the mol ratio DVB/RLi of DVB and organic single-lithium is 0.1～0.5, is preferably 0.2～0.4.Along with the raising of synthetic ratio DVB/RLi, initiator list lithium reduces, and many lithiums increase, when DVB/RLi＞0.5, and single lithium completely dissolve; When DVB/RLi＞1, initiator almost all is made up of many lithium dimers.
The used organic single-lithium of the present invention can be represented with RLi, wherein R is straight chain or branched alkyl, cycloalkyl or aryl, as can selecting lithium ethide, propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium, naphthyl lithium etc. for use, but preferably select n-Butyl Lithium or s-butyl lithium for use.
Additive in the initiator preparation process can be to contain the conjugated diolefine of 4～5 carbon atoms such as 1,3-butadiene, isoprene, also can be monovinylarene such as vinylbenzene, the 4-t-butyl styrene etc. that contain 8～12 carbon atoms.The mol ratio of additive and organic single-lithium is 2: 1～20: 1, but be preferably 5: 1～15: 1.
The preparation of initiator can be carried out in aliphatic hydrocarbon such as normal hexane, also can carry out in the mixed solvent of aliphatic hydrocarbon and naphthenic hydrocarbon.
The temperature of preparation initiator is generally 30～90 ℃.
Used mono vinyl arenes monomer contains 8～20 carbon atoms in the polymerization process, but preferably contain 8～12 carbon atoms, as can being on the vinylbenzene that replaces of vinylbenzene, alkyl or the vinyl substituent styrene derivatives to be arranged, the vinylbenzene that replaces as alkyl can from-select vinyl toluene, p-methylstyrene or the right-tert-butylbenzene ethene, the optional alpha-methyl styrene of substituent styrene derivatives is arranged on the vinyl.Mono vinyl arenes monomer can use separately, also can mix use.Consider from obtaining the complexity aspect, select vinylbenzene and p-methylstyrene better, select vinylbenzene best.
Used conjugate diene monomer contains 4～12 carbon atoms in the polymerization process, preferably contain 4～8 carbon atoms, as selecting 1, the 1,3-pentadiene of 3-divinyl, isoprene, 1,3-pentadiene, replacement or the divinyl of replacement, can be as the divinyl that replaces from 2, select in 3-dimethyl-1,3-butadiene, the 1-phenyl-1,3-butadiene.Conjugate diene monomer can use separately, also can mix use.Preferably select 1,3-butadiene or isoprene for use,, help industrialization because these two kinds of monomeric rates of polymerization are higher.
The solvent of polyreaction can be aromatic hydrocarbon, aliphatic hydrocarbon or naphthenic hydrocarbon, can select from benzene,toluene,xylene or ethylbenzene as aromatic hydrocarbon, and aliphatic hydrocarbon can be selected from hexane or heptane, and naphthenic hydrocarbon can be selected from pentamethylene, hexanaphthene or methylcyclohexane.These varsols can use separately, also can mix use, as optional aliphatic hydrocarbon and naphthenic hydrocarbon mixture-raffinating oil is polymer solvent.
Must remove in advance to deenergize for monomer above-mentioned and solvent and cause the impurity of initiator or active end inactivation, as the compound of water, oxygen, carbonic acid gas, sulphur and acetylene compound etc.
In polymerization process, can select for use Lewis bases compound to do polar additive and structure regulator, various Lewis bases compounds can be selected for use, but consider from obtaining the complexity aspect, preferably select for use ether compound or tertiary amine compound to do polar additive and structure regulator, can select tetrahydrofuran (THF), tetrahydropyrans or 1,4-dioxane for use as cyclic ether compounds; Aliphatic monoether can be selected Anaesthetie Ether or dibutyl ether for use; The optional spent glycol dme of aliphatic polyether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dibutyl ethylene glycol ether; Aromatic oxide can be selected diphenyl ether, methyl-phenoxide or similar ether for use; Tertiary amine compound can be selected triethylamine, 3 third ammonia, three fourth ammonia or other compound such as N for use, N, and N ', N '-tetramethyl-second diamino, N, N-ethyl phenylamino, pyridine or quinoline etc., the synthetic and synthetic used structure regulator of B section of A section can be identical, also can difference; Different structure regulators can be used alone, but also also mix together.
Polymeric reaction temperature is 0～150 ℃, and reaction better is preferably 50 ℃ between 40～70 ℃.
The consumption of initiator depends on the size of design molecular weight in the polymerization process.The consumption of general initiator is that per 100 gram monomers need add 0.8～2.5mmol lithium.
The invention still further relates to conjugated diolefine and monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, wherein with above-mentioned described method preparation
The a.A section is the random copolymerization section of monovinylarene and conjugated diolefine, and wherein the content of monovinylarene is 1～15%, and contents of ethylene is 20～50% in the conjugated diolefine chain;
The b.B section also is the random copolymerization section of monovinylarene and conjugated diolefine, and wherein the content of monovinylarene is 20～35%, and contents of ethylene is 40～65% in the conjugated diolefine chain.
The difference of monovinylarene content is greater than 10% among two sections of c.A, the B, and the difference of contents of ethylene is greater than 20% in the conjugated diolefine chain;
The d.A section accounts for 10～90% of multipolymer weight percentage;
E. the total content of monovinylarene is 10～40% in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and the content of vinyl is 30～50% in the conjugated diolefine chain.
With A section in the conjugated diolefine of method of the present invention preparation and the monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is the random copolymerization section of monovinylarene and conjugated diolefine, wherein the content of monovinylarene is 1～15%, contents of ethylene is 20～50% in the conjugated diolefine chain, be 20～30% preferably, both all can be controlled by the addition of structure regulator THF, and the too high rolling resistance of product that will cause of ethylene content increases in monovinylarene content and the conjugated diolefine chain; The B section also is the random copolymerization section of monovinylarene and conjugated diolefine, wherein the content of monovinylarene is 20～50%, be 30～35% preferably, should be not less than 10% with the difference of the content of A section monovinylarene, B section monovinylarene content is by the weight ratio decision of two sections of the content of the content of monovinylarene in the multipolymer, A section monovinylarene and A, B, it is too small that B section monovinylarene content is crossed difference low or B section and A section monovinylarene content, will reduce the anti-slippery of product.B section monovinylarene too high levels will influence other physicals such as elasticity, hardness of product.Contents of ethylene is 40～65% in the B section conjugated diolefine chain, be 55～65% preferably, the difference of contents of ethylene should be not less than 20% in B section and the A section conjugated diolefine chain, it is too small that contents of ethylene is crossed difference low or B section and A section contents of ethylene in the B section conjugated diolefine chain, also all can reduce the anti-slippery of product.Contents of ethylene is too high in the B section conjugated diolefine chain, equally also can influence other physical and mechanical property such as elasticity, hardness of product; The A section accounts for 20～50% of multipolymer weight percentage, is preferably 30～50% to be preferably 30%; The total content of monovinylarene is 10～40% in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, is 20～40% preferably, and the total content of vinyl is 30～50% in the conjugated diolefine chain, is 40～50% preferably.
Monovinylarene in conjugated diolefine of the present invention and the monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock contains 8～20 carbon atoms, but preferably contain 8～12 carbon atoms, as can being on the vinylbenzene that replaces of vinylbenzene, alkyl or the vinyl substituent styrene derivatives to be arranged, the vinylbenzene that replaces as alkyl can from-select vinyl toluene, p-methylstyrene or the right-tert-butylbenzene ethene, the optional alpha-methyl styrene of substituent styrene derivatives is arranged on the vinyl.Consider from obtaining the complexity aspect, select vinylbenzene and p-methylstyrene better, select vinylbenzene best.
Conjugated diolefine in conjugated diolefine of the present invention and the monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock can be and contains 4～12 carbon atoms, preferably contain 4～8 carbon atoms, as selecting 1, the 1,3-pentadiene of 3-divinyl, isoprene, 1,3-pentadiene, replacement or the divinyl of replacement, can be as the divinyl that replaces from 2, select in 3-dimethyl-1,3-butadiene, the 1-phenyl-1,3-butadiene.Consider to select 1,3-butadiene or isoprene better from the industrialization aspect, select 1,3-butadiene best.
Conjugated diolefine and monovinylarene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock by the inventive method preparation have good anti-slippery and rolling resistance, are particularly suitable for making tire tread, can use separately, also can use with other rubber mix.
Can obtain molecular weight distributing index with method of the present invention is 1.1～2.0, and mooney viscosity is 37～60 Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks.
The present invention is further illustrated below in conjunction with embodiment, but not the office in these embodiment.
Initiator concentration records with two volumetrys among the embodiment, mooney viscosity records with day SMV-200 type instrument in island proper Tianjin, in styrene content and the divinyl chain 1, the 2-structural content is tested with U.S. Perkin-Elmer1760X type infrared spectrometer, the polymericular weight and the employing U.S. Perkin-Elmer gel permeation chromatograph test that distributes thereof, the physical and mechanical properties of rubber unvulcanizate is pressed the method for GB1192-82 and is measured, (frequency is 40.6HZ to the tan δ value of rubber unvulcanizate with the test of the Perkin-Elmer DMA-7E type viscoelastic spectrometer of the U.S., temperature is at-100～100 ℃, and heat-up rate is 2 ℃/minute).
Embodiment 1-9
Under the high pure nitrogen protection; the according to the form below proportioning is with hexanaphthene, 1; 3-divinyl, tetrahydrofuran (THF) (THF), Vinylstyrene join in the 500ml exsiccant saline bottle; after mixing; inject n-Butyl Lithium with syringe; behind reaction 30min under 70 ℃, generate the scarlet homogeneous phase solution, be the multi-chelate organolithium initiator of different DVB/RLi.The results are shown in Table 1.
Ratio of components is as follows:
Hexanaphthene (g) 160
1,3-butadiene (g) 11
THF(mmol) 80
DVB (mmol) changes
N-Butyl Lithium (mmol) 100 tables 1
Embodiment 10-16
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| DVB/RLi DVB feeding quantity (mmol) concentration (mol/L) | 0 0 0.30 | 0.10 10 0.28 | 0.15 15 0.28 | 0.20 20 0.26 | 0.25 25 0.26 | 0.30 30 0.27 | 0.40 40 0.27 | 0.50 50 0.26 | 0.60 60 0.25 |
Utilize the initiator of the different DVB/RLi that embodiment 1 obtains, the mol ratio of constant monomer and n-Butyl Lithium is carried out polyreaction by following ratio of components.
Ratio of components is as follows:
Hexanaphthene (kg) 4.0
1,3-butadiene (kg) 0.375
Vinylbenzene (kg) 0.125
THF(g) 0.36
N-Butyl Lithium (mmol) 5
Diethylene glycol dimethyl ether (mmol) 7.5
Antioxidant 264 5
The synthesis step of DVB/RLi variation polymkeric substance is as follows:
Under nitrogen protection, with hexanaphthene, vinylbenzene, tetrahydrofuran (THF) and 1, the 3-divinyl adds in the 10 liter stainless steel polymeric kettles successively, after mixing, be warming up to 50 ℃, under agitation add the multi-chelate organolithium compound polymerization reaction of different DVB/RLi, polymerization time is 25min, and polymerisation conversion is 30%; Adding diethylene glycol dimethyl ether then, to carry out the B section synthetic, and polymerization is 4 hours under same temperature; After polyreaction finishes, add terminator Virahol and antioxidant 264, glue obtains diblock butylbenzene copolymer product after condensing through water vapor, and corresponding production code member is respectively A-G, and the structural performance data that record copolymer product see Table 2.Comparative Examples 1
Under nitrogen protection, in the stainless steel cauldron of 10 liters, add the 4.0kg hexanaphthene successively, 0.125kg styrene monomer, 0.36g (5ml) tetrahydrofuran (THF), 0.375kg divinyl.Be warming up to 50 ℃, stir to tremble to mix down and add butyllithium 5.0mmol and begin A section building-up reactions.Polymerization temperature is 50 ℃, polymerization time is 25min, make polymerisation conversion reach 30%, under same temperature, add the 7.5mmol diethylene glycol dimethyl ether, beginning B section is synthetic, polymerization time is 60min, adds the 2ml Virahol at last and the 5g antioxidant 264 carries out termination reaction, and glue promptly gets the butylbenzene copolymer product (H) of diblock after through the water vapor cohesion.The structural performance data that record copolymer product see Table 2.Comparative Examples 2
Under nitrogen protection, in the stainless steel cauldron of 10 liters, add the 4.0kg hexanaphthene successively, 0.125kg styrene monomer, 0.36g (5ml) tetrahydrofuran (THF), 0.375kg divinyl.Be warming up to 50 ℃, stirring down, adding butyllithium 5.0mmol begins A section building-up reactions.Polymerization temperature is 50 ℃, polymerization time is 25min, make polymerisation conversion reach 30%, the diethylene glycol dimethyl ether that under same temperature, adds 7.5mmol, beginning B section is synthetic, and polymerization time is 60min, add the 0.625mmol tin tetrachloride and carry out linked reaction, reaction times is 60min, adds the 2ml Virahol at last and the 5g antioxidant 264 carries out termination reaction, and glue promptly gets the butylbenzene copolymer product (I) of diblock after through the water vapor cohesion.The structural performance data that record copolymer product see Table 2.
Table 2
| Experiment numbers | 1 | 2 | 3 | 4 | 5 | 6 | 7 | Comparative Examples 1 | Comparative Examples 2 |
| DVB/RLi production code member dispersion index HI styrene content, (wt%) contents of ethylene, (wt%) gel content, (wt%) mooney viscosity, (ML 1+4 100) | 0.10 A 1.15 26.3 48.7 0 37 | 0.15 B 1.18 25.8 48.8 0 40 | 0.20 C 1.23 26.1 49.2 0.02 41 | 0.25 D 1.34 26.2 49.6 0.02 41 | 0.30 E 1.46 26.3 49.6 0.076 43 | 0.40 F 1.64 28.4 51.6 0.077 48 | 0.50 G 1.89 26.1 49.0 0.090 55 | 0 H 1．10 27.5 47.6 0 20.2 | 0 1 1.55 27.5 47.6 0.065 45 |
The composition and the microtexture of the multipolymer of two sections of A, B see Table 3 among A～I.
The physical and mechanical property of A～I sees Table 4.The tan δ value of-10 ℃ and 50 ℃ sees Table 6 on the viscosity bullet of the A～I spectrum.The composition and the microtexture of A, two sections multipolymers of B among table 3 diblock butylbenzene copolymer A～H
Table 4 diblock butylbenzene copolymer A～I rubber unvulcanizate
*Physical and mechanical property
*The rubber unvulcanizate prescription is as follows:
| Production code member | The A section | The B section | Two sections of A, B's is poor | |||
| St wt％ | Cv wt％ | St wt％ Cv wt％ | St wt％ | Cv | ||
| wt％ | ||||||
| A B C D E F G H I | 14.38 14.74 14.55 14.26 14.53 14.99 14.10 15.19 15.19 | 27.58 28.14 27.03 33.68 27.08 28 27 35.68 32.26 32.26 | 30.24 30.03 30.28 30.62 30.64 30.01 30.45 34.80 34.80 | 64.34 62.96 63.88 57.10 63.16 63.19 58.84 55.34 55.34 | 15.86 15.32 15.73 16.36 15.61 15.02 16.35 19 61 19.61 | 34.76 34.82 36.85 23.42 36.08 34.92 23.16 23.08 23.08 |
| Production code member | A | B | C | D | E | F | G | H | I |
| Tensile strength (Mpa) 300% is stretched (Mpa) elongation (%) tension set (%) shore hardness tear strength (kg/cm) surely | 14.3 9.2 465 10 54 45 | 14.6 9.0 470 11 55 48 | 15.5 9.0 465 10 57 52 | 15.6 9.1 475 58 11 51 | 15.8 470 11 58 51 | 16.3 9.3 460 10 64 58 | 17.4 9.5 455 9.6 67 57 | 15.0 9.0 361 8.0 66 40 | 17.4 10.8 348 8.5 68 47 |
Styrene-butadiene rubber(SBR) 100
Zinc oxide 5.0
Stearic acid 2.0
Accelerant CZ 1.0
Anti-aging agent RD 1.0
Sulphur 1.7
High abrasion carbon black 45
Machine oil 5.0
Tan δ value under-10 ℃ and 50 ℃ of table 5 diblock butylbenzene copolymer A～I
| Production code member | A | B | C | D | E | F | G | H | I |
| -10℃ tanδ 50℃ tanδ | 0.54 0.11 | 0.53 0.10 | 0.55 0.11 | 0.55 0.10 | 0.55 0.10 | 0.55 0.10 | 0.56 0.10 | 0.52 0.14 | 0.55 0.13 |
By the data in the table as can be seen: can obtain branching, that molecular weight distribution is wide, that mechanical property is good, high wet-sliding resistant and low-rolling-resistance diblock solution polymerized butadiene styrene rubber without coupling with method of the present invention.
Claims (13)
1. the method for synthetic 1,3-butadiene and styrenic diblock copolymer comprises successively:
(1) adds inert solvent, 1,3-butadiene, vinylbenzene, structure regulator, then, add multi-chelate organolithium initiator, in the presence of initiator, carry out the A section and synthesize, make polymerisation conversion reach 10～90%
(2) add structure regulator, carry out the B section and synthesize;
(3) after polyreaction finishes, add terminator and anti-aging agent, and condense;
Wherein A section and B section are 1,3-butadiene and cinnamic random copolymerization section, just these two kinds monomeric content differences in these two sections;
Wherein multi-chelate organolithium initiator is to be reacted in varsol by Vinylstyrene and organic single-lithium to make; Structure regulator is ether compound or tertiary amine compound; Cinnamic consumption is 10～40wt%; Polymeric reaction temperature is 0～150 ℃.
2. method according to claim 1 is characterized in that described polymerisation conversion is 20%～50%.
4. method according to claim 1 is characterized in that Vinylstyrene is 1,3-Vinylstyrene, 1,4-Vinylstyrene or their mixture.
5. method according to claim 1, the mol ratio that it is characterized in that Vinylstyrene and organic single-lithium is 0.1～0.5.
6. method according to claim 5, the mol ratio that it is characterized in that Vinylstyrene and organic single-lithium is 0.2～0.4.
7. method according to claim 1 is characterized in that described inert solvent is the mixture of aromatic hydrocarbon, aliphatic hydrocarbon, naphthenic hydrocarbon or naphthenic hydrocarbon and aliphatic hydrocarbon.
8. method according to claim 1 is characterized in that described ether compound is tetrahydrofuran (THF) or diethylene glycol dimethyl ether.
9. method according to claim 1 is characterized in that A section structure regulator synthetic and that the B section is synthetic used is identical or different; Different structure joint agent or use or mixing use separately.
10. method according to claim 1 is characterized in that polymeric reaction temperature is 40～70 ℃.
11. method according to claim 10 is characterized in that polymeric reaction temperature is 50 ℃.
12. the polymkeric substance according to any one described method preparation in the claim 1～11 is 1,3-butadiene and styrenic diblock copolymer, it is characterized in that:
The a.A section is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 1～15%, and contents of ethylene is 20～50% in the 1,3-butadiene chain;
The b.B section also is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 20～35%, and contents of ethylene is 40～65% in the 1,3-butadiene chain;
The difference of styrene content is greater than 10% among two sections of c.A, the B, and the difference of contents of ethylene is greater than 20% in the 1,3-butadiene chain;
The d.A section accounts for 10～90% of multipolymer weight percentage;
E. cinnamic total content is 10～40% in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and the content of vinyl is 30～50% in the 1,3-butadiene chain.
13. 1,3-butadiene according to claim 12 and styrenic diblock copolymer is characterized in that:
The a.A section is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 1～15%, and contents of ethylene is 20～30% in the 1,3-butadiene chain;
The b.B section also is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 30～35%, and contents of ethylene is 55～65% in the 1,3-butadiene chain;
The difference of styrene content is greater than 10% among two sections of c.A, the B, and the difference of contents of ethylene is greater than 20% in the 1,3-butadiene chain;
The d.A section accounts for 20～50% of multipolymer weight percentage;
E. cinnamic total content is 20～40% in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and the content of vinyl is 40～50% in the 1,3-butadiene chain.
14. 1,3-butadiene according to claim 13 and styrenic diblock copolymer is characterized in that:
The a.A section is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 1～15%, and contents of ethylene is 20～30% in the 1,3-butadiene chain;
The b.B section also is the random copolymerization section of vinylbenzene and 1,3-butadiene, and wherein cinnamic content is 30～35%, and contents of ethylene is 55～65% in the 1,3-butadiene chain;
The difference of styrene content is greater than 10% among two sections of c.A, the B, and the difference of contents of ethylene is greater than 20% in the 1,3-butadiene chain;
The d.A section accounts for 30% of multipolymer weight percentage;
E. cinnamic total content is 20～40% in the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and the content of vinyl is 40～50% in the 1,3-butadiene chain.
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| CN97121853A CN1062276C (en) | 1997-12-09 | 1997-12-09 | Conjugate diolefin and mono-vinyl arene two-block copolymer and its synthesis method |
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| CN97121853A CN1062276C (en) | 1997-12-09 | 1997-12-09 | Conjugate diolefin and mono-vinyl arene two-block copolymer and its synthesis method |
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| CN1118493C (en) * | 1999-02-24 | 2003-08-20 | 北京燕山石油化工公司研究院 | Process for preparing atactic copolymer of conjugated diene and monovinyl arylhydrocarbon |
| US6462137B2 (en) * | 2000-10-19 | 2002-10-08 | China Petroleum And Chemical Corporation | Star-block interpolymers and preparation of the same |
| JP5552025B2 (en) * | 2010-10-29 | 2014-07-16 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire |
| CN104628898A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Olefin polymerization termination method |
| KR101879527B1 (en) * | 2014-05-16 | 2018-07-18 | 크레이튼 폴리머즈 유.에스. 엘엘씨 | Branched broad mwd conjugated diene polymer |
| CN104693388A (en) * | 2014-12-31 | 2015-06-10 | 大连海事大学 | Preparation method for wide temperature region damping rubber of gradual change block structure through anion method |
| CN106700128B (en) * | 2015-07-22 | 2019-02-19 | 中国石油化工股份有限公司 | Rubber antioxidant and its application and solution polymerized butadiene styrene rubber and preparation method thereof |
| CN106832402B (en) * | 2015-12-04 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of thermoplastic elastomer (TPE) and preparation method thereof |
| CN107474464B (en) * | 2016-06-07 | 2020-10-23 | 中国石油化工股份有限公司 | Poly-conjugated diene/SBS composite rubber particle, preparation method thereof and application of composite rubber particle in modified asphalt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056695A (en) * | 1990-05-16 | 1991-12-04 | 阿托化学公司 | Make the method for transparent and shock proof styrene resin |
| CN1120342A (en) * | 1993-03-30 | 1996-04-10 | 国际壳牌研究有限公司 | Process for the preparation of a block copolymer composition and block copolymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056695A (en) * | 1990-05-16 | 1991-12-04 | 阿托化学公司 | Make the method for transparent and shock proof styrene resin |
| CN1120342A (en) * | 1993-03-30 | 1996-04-10 | 国际壳牌研究有限公司 | Process for the preparation of a block copolymer composition and block copolymer composition |
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