CN104672360A - Preparation method of modified syndiotactic-1,2-polybutadiene rubber - Google Patents
Preparation method of modified syndiotactic-1,2-polybutadiene rubber Download PDFInfo
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- CN104672360A CN104672360A CN201310621765.2A CN201310621765A CN104672360A CN 104672360 A CN104672360 A CN 104672360A CN 201310621765 A CN201310621765 A CN 201310621765A CN 104672360 A CN104672360 A CN 104672360A
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Abstract
The invention discloses a preparation method of modified syndiotactic-1,2-polybutadiene rubber. The preparation method is characterized by comprising the following steps: (1) preparing a syndiotactic-1,2-polybutadiene catalyst; and (2) preparing syndiotactic-1,2-polybutadiene rubber. According to the preparation method, an in-situ polymerization reaction is performed under the protection of high-purity N2, the molecular weight of a polymerization product is effectively reduced, the monomer conversion rate is greater than 86% after polymerization, and the content of microscopic 1,2-structures is greater than 98%. Hexane serves as a solvent, so that the environmental protection property is strong and the cost is low; and the activity of a catalytic system can be improved remarkably, the molecular weight of the polymerization product is effectively reduced, the cold flow property, wet-skid resistance and aging resistance of a polymer are improved.
Description
Technical field
The invention belongs to the manufacture technology field of rubber, be specifically related to the preparation method with-1,2-polybutadiene rubber between a kind of modification.
Background technology
Polybutadiene rubber has the advantages such as anti-slippery is good, ageing-resistant, low-heat-generation, can be used to make aircraft and doughnut.In addition with the difference of microtexture and relative molecular mass, 1, the application of 2-polyhutadiene in many fields such as plastics, coating, tackiness agent, functional polymer is increasingly extensive, can be used for the properties-correcting agent etc. preparing film, fiber, rubber item and rubber item.
Divide by the catalyst system of liquid polybutadiene rubber, be generally divided into sodium system, lithium system, transition metal (iron, cobalt, Nie, Chrome) system and rare-earth system; Sodium system catalyst system synthetic fluid polybutadiene rubber, except catalytic efficiency is lower, also exists that catalyzer composition is complicated, technique is loaded down with trivial details, 1,2 structural contents are higher in gained rubber problem; Other catalyst system as utilize transition metals cobalt, Nie, Chrome compound or complex compound etc. as catalytic active center, although can binary system be prepared into, but polymer solvent is still limited as benzene, toluene or dimethylbenzene, the problem of non-ambient close friend is not still resolved.
Between with-1,2-polyhutadiene be a kind of superpolymer simultaneously with plastics and rubber properties, from its come out since just cause people to pay close attention to widely.Its performance depends on a normality, and between low tone normality, same-1,2-polyhutadiene is elastomerics, and between height, between normality, same-1,2-polyhutadiene is a kind of semi-crystalline plastic.Activity with the most of catalyst system of-1,2-polyhutadiene between current synthesis is lower, and product 1,2-structural content is lower, and a normality is little, is difficult to the degree of crystallinity controlling polymerisate.
Co series catalysts is with-1 between synthesis, the system that 2-polyhutadiene taxis is very high is the first-selected catalyzer with-1,2-polyhutadiene between the high regularity of synthesis, its principal feature is as follows: homogeneous phase and heterogeneous Co compound are all the catalyzer that vertical structure has rule, such as Co (C
5h
7o
2)
2(C
5h
7o
2)
3, CoCl
2with the complex compound of ether, amine or pyridine, the inner complex of various cobalt and organic and mineral acid cobalt.Co catalyst system all forms homogeneous phase solution in normal hexane, hydrogenated gasoline and toluene equal solvent, and insoluble inorganic salt are as CoSO
4and CoCl
2react can form homogeneous complex with aluminum alkyls.When Co series catalysts adopts not halogen-containing aluminum alkyls to do promotor, the polyhutadiene of high 1,2-structure can be obtained.
Summary of the invention
The object of the present invention is to provide the preparation method with-1,2-polybutadiene rubber between a kind of modification, be greater than 86% through monomer after polymerization transformation efficiency, microcosmic 1,2-structural content is greater than 98%, and the feature of environmental protection is good, cost, improve the cold flow properties of polymkeric substance, anti-slippery and ageing resistance simultaneously.
The technical scheme that the present invention takes is:
With the preparation method of-1,2-polybutadiene rubber between a kind of modification, it is characterized in that, described preparation method comprises the steps:
(1) between system with-1,2-polyhutadiene catalyzer: vacuumized by polymerizer, cools pressurize under nitrogen effect, adds the hydrogenated gasoline solution of component A, B component, component C successively, grind 2 days under nitrogen protection, after 0 DEG C of ageing 60-80min, be warmed up to 10 DEG C of ageing 4-4.5h;
(2) between system with-1; 2-polybutadiene rubber: above-mentioned catalyzer is added in mill; under nitrogen protection, mill roll spacing is set in 1-1.3mm, controls mill roller temperature and remain 30-40 DEG C; the hexane solution of divinylic monomer is added in the reactor that the band of vacuum nitrogen gas disposal stirs; add the ethanolic soln of anti-aging agent again, control polymeric reaction temperature is 50-60 DEG C, and the reaction times is 5-6h; obtain between liquid modifying with-1,2-polybutadiene rubber.
Component A in above-mentioned steps (1): triisobutyl aluminium; B component: cobalt naphthenate; Component C: dithiocarbonic anhydride.
In above-mentioned steps (1), the ratio of the amount of substance of component A, B, C is n (B)/n (C)/n (A)=30:15:1, and monomer conversion is greater than 86%.
Above-mentioned anti-aging agent 2,6-ditertbutylparacresol or 2, the one in 2 '-methylene-bis (4-methyl-6-tert.-butyl phenol).
Beneficial effect of the present invention:
The present invention carries out home position polymerization reaction under high-purity N 2 is protected, and can significantly improve the activity of catalyst system, and effectively reduce the molecular weight of polymerisate, be greater than 86% through monomer after polymerization transformation efficiency, microcosmic 1,2-structural content is greater than 98%.Solvent is hexane, reduces noxious solvent to harm that is personal and environment, decreases the production cost brought by solvent recuperation process; The activity of catalyst system can be significantly improved, effectively reduce the molecular weight of polymerisate, improve the cold flow properties of polymkeric substance, anti-slippery and ageing resistance.
Embodiment
Embodiment 1
With the preparation method of-1,2-polybutadiene rubber between a kind of modification, it is characterized in that, described preparation method comprises the steps:
(1) between system with-1,2-polyhutadiene catalyzer: polymerizer is vacuumized, pressurize is cooled under nitrogen effect, add the solution containing 0.1mol triisobutyl aluminium successively, and then add 3mol loading type cobalt naphthenate, finally add 1.5mol dithiocarbonic anhydride, grind 2 days under nitrogen protection, after 0 DEG C of ageing 70min, be warmed up to 10 DEG C of ageing 4.5h;
(2) between system with-1; 2-polybutadiene rubber: add in mill by above-mentioned catalyzer, under nitrogen protection, is set in 1.1mm by mill roll spacing; control mill roller temperature and remain 30 DEG C; in the reactor that the band of vacuum nitrogen gas disposal stirs, add the hexane solution that 2L concentration is the divinyl of 5mol/L, then add the ethanolic soln of 2,6-ditertbutylparacresol; controlling polymeric reaction temperature is 50 DEG C; reaction times is 6h, obtains between liquid modifying with-1,2-polybutadiene rubber.
Embodiment 2
With the preparation method of-1,2-polybutadiene rubber between a kind of modification, it is characterized in that, described preparation method comprises the steps:
(1) between system with-1,2-polyhutadiene catalyzer: polymerizer is vacuumized, pressurize is cooled under nitrogen effect, add the solution containing 0.1mol triisobutyl aluminium successively, and then add 3mol loading type cobalt naphthenate, finally add 1.5mol dithiocarbonic anhydride, grind 2 days under nitrogen protection, after 0 DEG C of ageing 80min, be warmed up to 10 DEG C of ageing 4h;
(2) between system with-1; 2-polybutadiene rubber: above-mentioned catalyzer is added in mill; under nitrogen protection; mill roll spacing is set in 1-1.3mm; control mill roller temperature and remain 35 DEG C; the hexane solution that 2L concentration is the divinyl of 5mol/L is added in the reactor that the band of vacuum nitrogen gas disposal stirs; add 2 again; the ethanolic soln of 2 '-methylene-bis (4-methyl-6-tert.-butyl phenol); controlling polymeric reaction temperature is 55 DEG C; reaction times is 5.5h, obtains between liquid modifying with-1,2-polybutadiene rubber.
Claims (4)
1. between a modification with the preparation method of-1,2-polybutadiene rubber, it is characterized in that, described preparation method comprises the steps:
(1) between system with-1,2-polyhutadiene catalyzer: vacuumized by polymerizer, cools pressurize under nitrogen effect, adds the hydrogenated gasoline solution of component A, B component, component C successively, grind 2 days under nitrogen protection, after 0 DEG C of ageing 60-80min, be warmed up to 10 DEG C of ageing 4-4.5h;
(2) between system with-1; 2-polybutadiene rubber: above-mentioned catalyzer is added in mill; under nitrogen protection, mill roll spacing is set in 1-1.3mm, controls mill roller temperature and remain 30-40 DEG C; the hexane solution of divinylic monomer is added in the reactor that the band of vacuum nitrogen gas disposal stirs; add the ethanolic soln of anti-aging agent again, control polymeric reaction temperature is 50-60 DEG C, and the reaction times is 5-6h; obtain between liquid modifying with-1,2-polybutadiene rubber.
2. between a kind of modification according to claim 1 with the preparation method of-1,2-polybutadiene rubber, it is characterized in that, component A in described step (1): triisobutyl aluminium; B component: cobalt naphthenate; Component C: dithiocarbonic anhydride.
3. between a kind of modification according to claim 1 with-1, the preparation method of 2-polybutadiene rubber, it is characterized in that, in described step (1), the ratio of the amount of substance of component A, B, C is n (B)/n (C)/n (A)=30:15:1, and monomer conversion is greater than 86%.
4. between a kind of modification according to claim 1 with-1, the preparation method of 2-polybutadiene rubber, is characterized in that, described anti-aging agent 2,6-ditertbutylparacresol or 2, the one in 2 '-methylene-bis (4-methyl-6-tert.-butyl phenol).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085303A (en) * | 2021-12-21 | 2022-02-25 | 青岛科技大学 | Catalytic system, application thereof and preparation method of syndiotactic 1, 2-polybutadiene |
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2013
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085303A (en) * | 2021-12-21 | 2022-02-25 | 青岛科技大学 | Catalytic system, application thereof and preparation method of syndiotactic 1, 2-polybutadiene |
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Application publication date: 20150603 |