CN1069906C - Multi-chelate organolithium initiator and its method in synthesizing polymer with wide molecular weight distribution and high Mooney viscosity with the same - Google Patents
Multi-chelate organolithium initiator and its method in synthesizing polymer with wide molecular weight distribution and high Mooney viscosity with the same Download PDFInfo
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Abstract
The present invention relates to a method for using multiple-chelate type organic lithium as initiating agents for synthesizing the homopolymers or copolymers of conjugated diene and single vinyl aromatic hydrocarbon. The present invention is characterized in that in the polymerization process, the addition quantities of DVB and coupling agents are controlled for ensuring that single lithium, bi-lithium and multiple lithium simultaneously exist in multiple-chelate type organic lithium, and homopolymers or copolymers simultaneously have wide molecular weight distribution and high mooney viscosity. The present invention also relates to a multiple-chelate type organic lithium initiating agent which comprises organic bi-lithium and organic multiple lithium generated by the reaction of organic single lithium and divinyl benzene(DVB) in hydrocarbon solvents.
Description
The present invention relates to a kind of multi-chelate organolithium initiator and uses thereof, more particularly, the method that relates to a kind of multi-chelate organolithium compound and synthesize wide molecular weight distribution, high Mooney viscosity polymkeric substance as initiator.
Mention the GB2 that has of multi-chelate organolithium initiator in the prior art, 124,228A.In this patent, obtain the multi-chelate organolithium compound by the reaction of Vinylstyrene (DVB) and s-butyl lithium, the mol ratio DVB of DVB and organolithium: RLi＞n: n+1 wherein, n 〉=2.Carrying out the molecular weight distribution that anionic polymerisation obtains with this initiator only is 1.1～1.4.
US3 has also mentioned this multi-chelate organolithium initiator in 644,322.Its preparation is carried out in two steps, at first conjugated dienes and organic single-lithium----s-butyl lithium reaction, and then the reaction of the adding DVB and the first step makes the multi-chelate organolithium compound.
At US3, DVB uses as coupling agent in 280,084, and its adds polyreaction is finished after usually, also can before the polyreaction or with n-Butyl Lithium reaction formation seed initiator after add.Do not mention the particular content of seed initiator in this patent.
EP 0,573, and among 893 A2, DVB joins in the polymerization reaction system with divinyl, vinylbenzene, hexanaphthene, n-Butyl Lithium etc. as reaction raw materials.Add the polyfunctional group coupling agent again after polyreaction finishes polymkeric substance is carried out branching, to obtain the polymeric articles of wide molecular weight distribution.
What above-mentioned prior art was related all is to adopt multi-chelate organolithium initiator to prepare the method for the polymkeric substance of wide molecular weight distribution, but the applicant finds prior art or adopts the method for all raw material one step addings, this can make the polyreaction complexity, and micmstructure of polymer is difficult to control; Perhaps select for use vivaciously, be difficult for the s-butyl lithium of storing; Perhaps select DVB/RLi ratio greater than 0.5, the molecular weight distribution of this meeting limit polymerization thing.
In order to overcome the weak point that prior art exists, the present invention at first prepares the multi-chelate type seed initiator, and then, can avoid occurring DVB and add fashionable reaction complexity and the unmanageable situation of micmstructure of polymer with other raw materials by the seed initiator initiated polymerization; Secondly, it is the synthetic seed initiator of raw material that the present invention selects the n-Butyl Lithium of cheap and stable performance for use, has reduced cost; In preparation seed initiator process, we select DVB/RLi＜0.5 because when DVB/RLi＞0.5, molecular weight distribution is narrowed down, and when reaction later stage coupling, can make polymeric system viscosity excessive and produce crosslinked, the increase gel content; In addition, in the polymer reaction later stage, we adopt SnCl
4Carry out coupling, find increase, can not only add wide molecular weight distribution, and can increase the mooney viscosity of polymkeric substance along with the Sn/RLi value.
The purpose of this invention is to provide a kind of multi-chelate organolithium, it can maintain single lithium, two lithium and many lithiums and exists simultaneously during whole polyreaction, make molecular weight distribution wideer, more even.
Another object of the present invention is to use multi-chelate organolithium compound of the present invention as the synthetic wide molecular weight distribution of initiator, high Mooney viscosity polymkeric substance.
Other purpose of the present invention and advantage from following explanation as can be seen.
The present invention relates to a kind of is the method for initiator synthesis of conjugate diene and monovinylarene homopolymer or multipolymer with the multi-chelate organolithium, it is characterized in that the add-on by control DVB and coupling agent guarantees to exist simultaneously in the multi-chelate organolithium single lithium, two lithium and many lithiums and not only had homopolymer or the multipolymer that wide molecular weight distribution has high Mooney viscosity simultaneously in polymerization process.
The invention still further relates to a kind of multi-chelate organolithium initiator, wherein contain organic single-lithium and in hydrocarbon solvent, react organic two lithiums and the organic many lithiums that generates with Vinylstyrene (DVB).
Multi-chelate organolithium initiator of the present invention is reacted in hydrocarbon solvent by DVB and organic single-lithium and obtains.In reaction process, add conjugated dienes or mono vinyl arenes monomer as additive,,, obtain the homogeneous initiator solution to improve the solubleness of initiator in the hydrocarbon solution so that on two lithiums and multi-lithium initiator molecule, form the polymkeric substance galianconism.
The preparation of multi-chelate organolithium initiator of the present invention is to finish in a step.
Multi-chelate organolithium initiator of the present invention is the mixture of organic single-lithium, two lithium and many lithium compounds, causing the polymkeric substance that obtains by it will be made up of the polymer molecule of corresponding single armed, both arms and multi-arm, and therefore the molecular weight distribution of polymkeric substance is widened.
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 preferably 0.2～0.4 between 0.1～0.5.Along with the raising of synthetic ratio DVB/RLi, single lithium reduces in the initiator, 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.
Organic single-lithium used among the present invention can be represented with RLi, wherein R is straight chain or branched alkyl, cycloalkyl or aryl, as can selecting n-Butyl Lithium, s-butyl lithium, lithium ethide, sec.-propyl lithium, phenyl lithium, 4-aminomethyl phenyl lithium, 2-naphthyl lithium, cyclohexyl lithium or the like, but preferably select n-Butyl Lithium and s-butyl lithium.
Additive in the initiator preparation process can be to contain the conjugated dienes 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, normal heptane or naphthenic hydrocarbon such as hexanaphthene, also can carry out in the mixed solvent of aliphatic hydrocarbon and naphthenic hydrocarbon.
The temperature of preparation initiator is generally 30-90 ℃.
The conjugated dienes monomer contains 4～12 carbon atoms in the polymerization process, preferably contain 4～8 carbon atoms, as selecting 1,3-butadiene, isoprene, mono vinyl arenes monomer can select to contain 8～20 carbon atoms, but preferably contains the vinylbenzene of 8～12 carbon atoms or the vinylbenzene that alkyl replaces.
It is more favourable carrying out polyreaction in aliphatic hydrocarbon or naphthenic hydrocarbon.Be polymer solvent as selecting normal hexane, normal heptane, hexanaphthene and raffinating oil.The present invention selects for use and raffinates oil as polymerization solvent is to compare with hexanaphthene because of it, the source is wide, price is low, zero pour is low, do not need tracing thermal-insulating winter when in pipeline, carrying, and, with raffinate oil the synthetic polymer performance with not significantly difference of hexanaphthene.
In order further to widen the molecular weight distribution of polymkeric substance, it is necessary that the reactive polymer molecule that obtains is carried out linked reaction.The adding of coupling agent makes the different reactive polymer molecular moiety generation linked reaction of arm number, generates the more coupling polymer molecule of arm number, and molecular weight distributing index is further improved.Along with the increase of coupling agent and organic single-lithium mol ratio, the molecular weight distribution of polymkeric substance is further widened, but gel content also will raise.Therefore, the mol ratio of coupling agent and organic single-lithium is preferably in 0.1～0.125 scope between 0.05～0.20, and coupling agent can be selected silicon tetrachloride, tin tetrachloride, diethylene adipate, dimethyl adipate etc. for use, and best choice is a tin tetrachloride.
In the process of preparation randomly solution polymerized butylbenzene, can select tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc. as polar additive and structure regulator, best choice is a tetrahydrofuran (THF).
Polymeric reaction temperature is 50～80 ℃.
The consumption of initiator depends on the size of design molecular weight in the polymerization process.The consumption of general initiator is that every 100g monomer need add 0.8～2.5mmol lithium.
The molecular weight distributing index that adopts method of the present invention can obtain polymkeric substance is 2.30～3.49.
After DVB/RLi and Sn/RLi determined, the mooney viscosity of polymkeric substance was main with to design molecular weight relevant.The design molecular weight that is used for oil-filled high Mooney polymkeric substance is 6 * 10
4～1.2 * 10
5Between, be preferably 8 * 10
4～1.0 * 10
5Under this molecular weight, the mooney viscosity of polymkeric substance is 81-162.
The wide molecular weight distribution high Mooney viscosity solution polymerized butylbenzene glue that obtains according to the method described above can use separately, also can fill 500 of 20～40phr
#The oil-extended styrene-butadiene rubber that high aromatic oil obtains excellent property and serves many purposes.
The following examples will help illustrating the present invention, but not limit to its scope.
Embodiment 1
Under high purity nitrogen protection; the according to the form below proportioning is with hexanaphthene, 1; 3-divinyl, tetrahydrofuran (THF) (THF), Vinylstyrene (DVB) 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.Initiator concentration records with two volumetrys.The results are shown in Table 1.Ratio of components:
Hexanaphthene (g) 160
1,3-butadiene (g) 11
THF(mmol) 80
DVB (mmol) changes
N-Butyl Lithium (mmol) 100 tables 1
Embodiment 2
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| DVB/RLi DVB feeding quantity (mmol) concentration (mol/L) | 0 0 0.30 | 0.1 10 0.28 | 0.15 15 0.28 | 0.2 20 0.26 | 0.25 25 0.26 | 0.3 30 0.27 | 0.4 40 0.27 | 0.5 50 0.26 | 0.6 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:
(ml) 7000 raffinates oil
1,3-butadiene (g) 600
Vinylbenzene (g) 200
THF(ml) 25
N-Butyl Lithium (mmol) 10
The synthesis step of DVB/RLi variation polymkeric substance is as follows:
Under the high pure nitrogen protection; to raffinate oil, 1; 3-divinyl, vinylbenzene, THF join in the stainless steel polymeric kettle of 10 liter bands stirring; be warmed up to 70 ℃ with hot water by chuck; the multi-chelate organolithium initiator that adds different DVB/RLi. at 70 ℃ of following polyase 13 0min; with 8 grams 2; the 6-di-tert-butyl-4-methy phenol is dissolved in 1: 1, and the Virahol of (volume ratio) and toluene solution stop polyreaction; obtain random butylbenzene copolymer product after the water vapor cohesion, the molecular weight distributing index that records multipolymer is as shown in table 2.Table 2
*Molecular weight distributing index records with GPC.
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| The DVB/RLi dispersion index * | 0 1.04 | 0.1 1.17 | 0.15 1.24 | 0.2 1.35 | 0.25 1.51 | 0.3 1.62 | 0.4 1.41 | 0.5 1.37 | 0.6 1.36 |
By data in the table as can be seen, the molecular weight distributing index that causes the polymerisate obtain with multi-chelate organolithium initiator increases with the increase of DVB/RLi earlier, but when DVB/RLi＞0.3, molecular weight distributing index reduces on the contrary.
Embodiment 3
Utilize the initiator of the different DVB/RLi that embodiment 1 obtains, constant monomer and n-Butyl Lithium mol ratio are carried out polyreaction by following ratio of components.Ratio of components:
(ml) 7000 raffinates oil
1,3-butadiene (g) 600
Vinylbenzene (g) 200
THF(ml) 25
N-Butyl Lithium (mmol) 10
DVB/RLi changes
Tin tetrachloride (mmol) changes
It is as follows that Sn/RLi changes experimental procedure:
Under high pure nitrogen protection, with raffinate oil, 1,3-butadiene, vinylbenzene, THF join in the stainless steel polymeric kettle that 10 liter bands stir, and is warmed up to 70 ℃ with hot water by chuck, adds the multi-chelate organolithium initiator of different DVB/RLi.At 70 ℃ of following polyase 13 0min, adding afterwards causes the different tin tetrachloride of Sn/RLi mol ratio to carry out linked reaction, restrain 2 with 8 behind the 30min, the 6-di-tert-butyl-4-methy phenol is dissolved in 1: 1, and the Virahol of (volume ratio) and toluene solution stop polyreaction, obtain random butylbenzene copolymer product after the water vapor cohesion, it is as shown in table 3 that GPC records the molecular weight distributing index of multipolymer.Table 3
| Numbering | 10 11 12 13 14 15 | 16 17 18 19 20 21 |
| DVB/RLi | 0 | 0.20 |
| The Sn/RLi dispersion index | 0 0.05 0.10 0.125 0.15 0.20 1.04 1.36 1.54 1.56 1.70 --- | 0 0.05 0.10 0.125 0.15 0.20 1.35 2.21 2.35 2.52 2.63 2.35 |
| Numbering | 22 23 24 25 26 27 | 28 29 30 31 32 33 |
| DVB/RLi | 0.25 | 0.30 |
| The Sn/RLi dispersion index | 0 0.05 0.10 0.125 0.15 0.20 1.51 1.81 2.30 3.49 2.08 1.82 | 0 0.05 0.10 0.125 0.15 0.20 1.62 1.88 3.34 2.78 2.35 gels |
| Numbering | 34 35 36 37 38 39 | 40 41 42 43 44 45 |
| DVB/RLi | 0.40 | 0.50 |
| The Sn/RLi dispersion index | 0 0.05 0.10 0.125 0.15 0.20 1.41 1.66 1.50 2.66 3.62 gels | 0 0.05 0.10 0.125 0.15 0.20 1.37 2.39 gel gel gel gels |
From tabular data as can be seen, the linear polymer molecule and the tin tetrachloride that adopt n-Butyl Lithium simple function group initiator to cause carry out forming the molecule that highest weight is four times in simple linear polymer after the coupling, molecular weight distributing index is up to 1.7, but adopt the multi-chelate organolithium initiator difference, the molecular weight distribution itself that obtains when using separately is just than broad, after adopting the tin tetrachloride coupling, increase along with Sn/RLi, molecular weight distribution is widened, and DVB/RLi is between 0.2～0.3, Sn/RLi can obtain the solution polymerized butylbenzene of molecular weight distributing index wide distribution between 2.30～3.49 in 0.1～0.125 scope.Embodiment 4
Experimental procedure is with embodiment 3, and the reaction ratio of components is as follows: ratio of components:
(ml) 7000 raffinates oil
1,3-butadiene (g) 600
Vinylbenzene (g) 200
THF(ml) 25
N-Butyl Lithium (mmol) 7
DVB/RLi 0.25,0.30
Tin tetrachloride (mmol) changes
Sn/RLi changes
The mooney viscosity of the solution polymerized butylbenzene glue that experiment obtains and the relation of DVB/RLi and Sn/RLi are listed in table 4.Table 4
*Day island proper Tianjin SMV-200 type instrument is adopted in the mooney viscosity test.
| Numbering | 46 47 48 49 | 50 51 52 53 | 54 55 56 57 |
| DVB/RLi | 0 | 0.25 | 0.30 |
| Sn/RLi ML 1+4 100 * | 0 0.05 0.10 0.125 1 42 37 32 | 0 0.05 0.10 0.125 ＜15 44 65 71 | 0 0.05 0.10 0.125 ＜30 45 75 105 |
As can be seen from Table 4, when the design molecular weight was identical, the mooney viscosity of the basic glue that obtains increased with the increase of DVB/RLi, and when design molecular weight and all timings of DVB/RLi, the mooney viscosity of basic glue further increases with the increase of tin tetrachloride add-on.
Embodiment 5
Implementation step is carried out polyreaction with embodiment 3 by following ratio of components.Ratio of components:
(ml) 7000 raffinates oil
1,3-butadiene (g) 600
Vinylbenzene (g) 200
THF(ml) 25
N-Butyl Lithium (mmol) changes
DVB/RLi 0.25,0.30
Tin tetrachloride (mmol) changes
Sn/RLi 0.125
The performance perameter of the solution polymerized butylbenzene glue that experiment obtains is listed in table 5.Table 5
| Numbering | 58 59 | 60 61 62 63 |
| DVB/RLi | 0.2 | 0.3 |
| Design molecular weight (MA * 10 4) dispersion index gel content (%) *Limiting viscosity [η] **Mooney viscosity [ML 1+4 100] | 8.0 10.0 2.1 2.3 0.04 0.20 317 354 148 162 | 4.0 6.0 7.0 8.0 2.51 2.87 2.37 2.3 0.06 0.10 0.10 0.20 203 222 293 312 94 105 138 156 |
*The mensuration of gel content: take by weighing about 0.5g glue sample, be placed in the 400 purpose stainless (steel) wires and after 24 hours, use the toluene extracting more than 48 hours again, survey the content of insolubles with analytical balance with the toluene immersion.
Gel content (%)=(insolubles weight/samples weighed) * 100
*Limiting viscosity records with Ubbelohde viscometer.
From tabular data as can be seen, when DVB/RLi and Sn/RLi one timing, the mooney viscosity of polymkeric substance increases along with the increase of design molecular weight.
Carry out the test of physical and mechanical properties to being numbered 60～63 solution polymerized butylbenzene glue, test result is listed in table 6.Table 6
| Numbering | 60 | 61 | 62 | 63 |
| Mooney viscosity [ML 1+4 100] tensile strength, (Mpa) 300% stretches surely, (Mpa) elongation, (%) tension set, (%) hardness, (Shao Shi A) second-order transition temperature Tg, (℃) | 94 17.1 12.2 400 14 66 -58 | 105 18.1 12.5 440 16 64 -58 | 138 17.9 11.5 440 14 64 -54 | 156 18.0 11.7 420 10 66 -58 |
As can be seen from Table 6, when mooney viscosity was higher, indexs such as the tensile strength of cross-linked rubber, stress at definite elongation, hardness changed little, but the basic glue of wide molecular weight distribution, high Mooney viscosity has very big value to producing oil-filled solution polymerized butylbenzene glue.
Embodiment 6
With mooney viscosity is that 94～156 four kinds wide distribution high Mooney solution polymerized butylbenzene glue are basic glue, fills 37.5sphr 500
#The physical and mechanical properties of the oil-filled cross-linked rubber of aromatic hydrocarbon oil is as shown in the table:
| Numbering | 64 | 65 | 66 | 67 |
| Basis glue Mooney viscosity vulcanizate Mooney viscosity hot strength (MPa) 300% is stretched (MPa) percentage elongation (%) permanent deformation (%) hardness (Shao Shi) tearing strength (kg/cm) surely | 94 41.7 16.1 11.0 412 14 64 37.6 | 105 48.2 16.7 11.1 440 16 62 38.8 | 138 38.9 16.4 11.9 424 16 64 38.8 | 156 39.3 16.2 11.9 396 12 66 36.1 |
Selection is numbered 65 oil-extended styrene-butadiene rubber and is applied in the prescription of tread rubber and tube glue the physical and mechanical properties of its cross-linked rubber such as following table:
| Numbering | Tread rubber | Inner tube of a tyre degree |
| 65 (GB1192-82) GB | 65 (GB7036-89) GB | |
| Hot strength (MPa) 300% is stretched (MPa) percentage elongation (%) permanent deformation (%) hardness (Shao Shi) tearing strength (kg/cm) Akron abrasion proportion (g/cm surely3) | 17.9 16.6 10.0 / 500 450 12 / 64 / 63.4 45 0.07 0.4 1.13 / | 19.6 17.6 16.1 / 620 600 20 35 60 / 84 45 / / |
Oil-filled glue preparation process is as follows:
Ratio of components: 100 parts in basic glue
800 parts of hexanaphthenes
500
#37.5 parts of aromatic hydrocarbon oil
Process: in the 1000ml there-necked flask, basic glue is added virtue with hexanaphthene dissolving back
Hydrocarbon ils takes out after 2.5 hours 70 times stirrings, removes behind poach
Solvent is extruded drying, obtains oil-filled glue.
Below only illustrate with regard to embodiment of the present invention, this area professional is conspicuous in the various improvement of having done without prejudice to essence of the present invention after reading the present invention, all belongs to the claimed scope of the present invention.
Claims (21)
1. multi-chelate organolithium initiator, wherein this initiator prepares by following method: join in the mixture of hydrocarbon solvent and additive and make its reaction form the mixture that has organic single-lithium, organic two lithiums and organic many lithiums simultaneously so that the mol ratio of Vinylstyrene and organic single-lithium is 0.1～0.5 control mode with Vinylstyrene and organic single-lithium.
2. according to the initiator of claim 1, wherein organic single-lithium can be represented with RLi, and wherein R is n-Butyl Lithium, s-butyl lithium, lithium ethide, sec.-propyl lithium, phenyl lithium, 4-aminomethyl phenyl lithium, 2-naphthyl lithium, cyclohexyl lithium.
3. according to the initiator of claim 2, wherein organic single-lithium is a n-Butyl Lithium.
4. according to the initiator of claim 1, wherein additive is selected from 1,3-butadiene and vinylbenzene.
5. according to the initiator of claim 1, wherein the mol ratio of additive and organic single-lithium is 2: 1～20: 1.
6. according to the initiator of claim 5, wherein the mol ratio of additive and organic single-lithium is 5: 1～15: 1.
7. according to the initiator of claim 1, wherein hydrocarbon solvent is selected from the mixture of aliphatic hydrocarbon, naphthenic hydrocarbon or aliphatic hydrocarbon and naphthenic hydrocarbon.
8. according to the initiator of claim 1, wherein the mol ratio of Vinylstyrene and organic single-lithium is 0.2～0.3.
9. according to the initiator of claim 1, wherein said Vinylstyrene is 1,3-Vinylstyrene, 1,4-Vinylstyrene or its mixture.
10. the preparation method who possesses the homopolymer or the multipolymer of wide molecular weight distribution and high Mooney viscosity, comprising:
(1) so that the mol ratio of Vinylstyrene and organic single-lithium is 0.1～0.5 control mode with Vinylstyrene and organic single-lithium joins in the mixture of hydrocarbon solvent and additive and make its reaction;
The wherein Vinylstyrene that (2) will so obtain and the mol ratio of organic single-lithium are that 0.1～0.5 multi-chelate organolithium initiator mixture adds in conjugated dienes and the monovinylarene and reacting 30 minutes in the presence of polymerization solvent under 50～80 ℃.
11. according to the method for claim 10, wherein Vinylstyrene is 1,3-Vinylstyrene, 1,4-Vinylstyrene or its mixture.
12. according to the method for claim 10, wherein the mol ratio of Vinylstyrene and organic single-lithium is 0.2～0.3.
13. according to the method for claim 10, wherein the conjugated dienes monomer is a 1,3-butadiene, mono vinyl arenes monomer is a vinylbenzene.
14., wherein can select for use the mixture of aliphatic hydrocarbon, naphthenic hydrocarbon or aliphatic hydrocarbon and naphthenic hydrocarbon in the polymerization process as polymerization solvent according to the method for claim 10.
15., wherein select for use and raffinate oil as polymerization solvent according to the method for claim 14.
16., wherein also be included in polyreaction end back adding coupling agent and carry out linked reaction according to the method for claim 10.
17. according to the method for claim 16, wherein coupling agent is selected tin tetrachloride for use.
18. according to the method for claim 17, wherein the mol ratio Sn/RLi of tin tetrachloride and organic single-lithium is 0.05～0.20.
19. according to the method for claim 18, wherein the mol ratio Sn/RLi of tin tetrachloride and organic single-lithium is 0.1～0.125.
20. according to the method for claim 10, wherein polymeric reaction temperature is 70 ℃.
21., wherein select for use tetrahydrofuran (THF) as polar additive and structure regulator according to the method for claim 10.
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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 |
| CN110483862B (en) * | 2018-05-15 | 2023-03-31 | 中国石油化工股份有限公司 | Molecular chain multi-terminal multi-functional solution-polymerized styrene-butadiene rubber, preparation method thereof and application thereof in tire tread rubber material formula |
| CN110885412B (en) * | 2019-12-17 | 2023-01-06 | 广东众和高新科技有限公司 | Preparation method of SBS glue solution, star-shaped SBS prepared by preparation method and application of star-shaped SBS |
| CN113461837A (en) * | 2021-07-16 | 2021-10-01 | 广东众和高新科技有限公司 | Preparation method of low cis-high ethylene-based hydroxyl polybutadiene rubber |
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