CN103665227A - Preparation method of epoxidized 1, 2-polybutadiene - Google Patents
Preparation method of epoxidized 1, 2-polybutadiene Download PDFInfo
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- CN103665227A CN103665227A CN201310615492.0A CN201310615492A CN103665227A CN 103665227 A CN103665227 A CN 103665227A CN 201310615492 A CN201310615492 A CN 201310615492A CN 103665227 A CN103665227 A CN 103665227A
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Abstract
The invention relates to a preparation method of a polymeric material, in particular to a preparation method of epoxidized 1, 2-polybutadiene. Preparation steps of the preparation method are as follows: composition A and composition B are added to a reaction flask and stirred by magnetic force at the temperature of 65 DEG C until the composition A is dissolved; composition C and composition D are added to the reaction flask and stirred fully and uniformly; quantitative composition E is added to a system and reacted for a period at the constant temperature; after the reaction is finished, a product is poured out; absolute ethyl alcohol is added for precipitating a solid, sedimentation is performed for a period, suction filtration is performed, and a sodium bicarbonate solution and distilled water are used for washing a product solid for a plurality of times respectively; and the washed product solid is put into an oven for vacuum drying for 12 h at the temperature of 60 DEG C, and a product is obtained. The invention provides a synthesis method for epoxidizing 1, 2-polybutadiene. The prepared epoxidized 1, 2-polybutadiene can be used for toughening modification of other high polymer materials (such as nylon, epoxy resin and the like).
Description
Technical field
The present invention relates to a kind of preparation method of polymeric material, particularly relate to a kind of epoxidation 1, the preparation method of 2-polyhutadiene.
Background technology
Polyhutadiene is the conventional important polymer materials of a class, existence due to reactable Shuan Jianhuo functional group in molecule or in side chain, make it be able to extensively in fields such as coating, tamanori, cast rubber item, jointing material, rubber processing aids, be applied, particularly six the seventies are in space rocket solid fuel propelling agent since successful Application, developed rapidly, become an important class in polymkeric substance.But because 1,2-polyhutadiene molecular chain is simple carbon-chain structure, there is no polar group, limited to a certain extent its scope of application.For further improving the performance of 1,2-polyhutadiene, widen its Application Areas, it is carried out to chemical modification and day by day become developing direction active in rubber materials.
In numerous method of modifying, epoxidation modification has higher industrial value.Lv Xuemei, Huang Baochen etc. have studied the epoxidation modification (China Synthetic Rubber Industry, 2006-01-15,29(1) of low relative molecular weight Trans 1,4-Polybutadiene: 30 ~ 34).Li Ping, Zheng Yuansuo etc. have studied the epoxidation modification (supplementary issue 2 in 2009 for the research of epoxidation hydroxy-terminated polybutadienes modified epoxy heat insulating coat, material engineering) of hydroxy-terminated polybutadienes.Zhang little Hua, xuwei arrow etc. has been studied the epoxidation modification (the epoxidation research of terminal hydroxyl polybutadiene liquid rubber, thermosetting resin, in March, 2004, the 19th the 2nd phase of volume) of terminal hydroxyl polybutadiene liquid rubber.
The polyhutadiene that above-mentioned institute uses has two features: the one, and the molecular weight of polyhutadiene is all lower, and number-average molecular weight is all in 2000 left and right; The 2nd, polyhutadiene molecular structure is Isosorbide-5-Nitrae polymerization or has carried out terminal groups modification.The polyhutadiene that this experiment adopts is a kind of high molecular syndiotaxy 1, (Syndiotactic 1 for 2-polyhutadiene, 2-Polybutadiene), number-average molecular weight Mn is 1200000 left and right, between polyhutadiene, normality is in 25% left and right, 1,2 structural content is more than 95%, and degree of crystallinity is in 20% left and right.At present, have no the report to high molecular, syndiotaxy and the epoxidation modification that polyhutadiene of end group does not carry out, also have no the report of the technical indicator of the polyhutadiene after modification.
Summary of the invention
The object of the present invention is to provide a kind of epoxidation 1, the preparation method of 2-polyhutadiene, the method is a kind of high molecular syndiotaxy 1, (Syndiotactic 1 for 2-polyhutadiene, the synthetic method of epoxidation modification 2-Polybutadiene), preparation technology is simple, for new road has been opened up in the further application of polyhutadiene.Its performances such as anti-slippery, binding property, resistance to air loss and oil-proofness through the TPI of epoxidation modification sizing material (ETPI), have greatly been improved, using the aspect requirement that more can meet as high-performance tire material.
The object of the invention is to be achieved through the following technical solutions:
A kind of epoxidation 1, the preparation method of 2-polyhutadiene, described method comprises following preparation process:
A, component A and B component are added in reaction flask, in 65 ℃ of lower magnetic forces, be stirred to component A and dissolve, in reaction flask, add component C and D, stir, in system, add quantitative component E, under constant temperature, react for some time, after reaction finishes, product is poured out, added dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain product.
Described a kind of epoxidation 1, the preparation method of 2-polyhutadiene, described component A is high molecular syndiotaxy 1,2-polyhutadiene, number-average molecular weight Mn is 1200000, degree of crystallinity 20%, 1,2-structural content is greater than 95%.
Described a kind of epoxidation 1, the preparation method of 2-polyhutadiene, described B component is lower paraffin hydrocarbons or naphthenic hydrocarbon, comprises hexanaphthene, normal hexane.
Described a kind of epoxidation 1, the preparation method of 2-polyhutadiene, described component D is a kind of phase-transfer catalyst, structure is (CH
2cH
2o)
n.
Described a kind of epoxidation 1, the preparation method of 2-polyhutadiene, the mass concentration of described component A is 8g/dL, and the mass concentration ratio of component C and component A is Mc/Ma=21.5%, and the mol ratio of component C and component E is: C/E=1:1.
Advantage of the present invention and effect are:
Polydiolefin rubber after epoxidation modification, had both kept original structure and performance, had increased many new premium propertiess again because introduce new group in molecular chain.For example: the epoxidation of natural rubber can increase damping performance, improve the performance of wear resistance and moist tensile stress and cross-linked rubber hydrocarbon resistant solvent thereof.Epoxidised 1,2 one polyhutadiene has improved adhesion strength, thermostability and solvent resistance.Epoxidised polybutadiene latex is applied in resorcinol formaldehyde latex (RLF) dipping tyre cord.Both the feature that had kept the original low-rolling-resistance of TPI sizing material, compression heat generation and fatigue performance excellence through the TPI of epoxidation modification sizing material (ETPI), its performances such as anti-slippery, binding property, resistance to air loss and oil-proofness have greatly been improved again, using the each side requirement that more can meet as high-performance tire material.Visible, the polydiolefin rubber after epoxidation modification has good industrial prospect.
Fig. 1 is the infrared spectrogram of epoxidized polybutadiene of the present invention;
Fig. 2 is the H-NMR spectrum analysis of epoxidized polybutadiene of the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings.
By 15g polyhutadiene, 200ml hexanaphthene is put into 500ml there-necked flask, at 65 ℃, treat that polyhutadiene dissolves completely, in system, slowly add 3.2g formic acid, 0.6g polyoxyethylene glycol, after dropwising, reflect again 0.5 hour, in 3.2g hydrogen peroxide is in 20min, be slowly added drop-wise in system, under constant temperature, continue reaction 2 hours, after reaction finishes, product is poured out, add dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain white toughness product.
By 15g polyhutadiene, 200ml hexanaphthene is put into 500ml there-necked flask, at 65 ℃, treat that polyhutadiene dissolves completely, in system, slowly add 1.8 formic acid, 0.3g polyoxyethylene glycol, after dropwising, reflect again 0.5 hour, in 1.8g hydrogen peroxide is in 20min, be slowly added drop-wise in system, under constant temperature, continue reaction 2 hours, after reaction finishes, product is poured out, add dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain white toughness product.
By 10g polyhutadiene, 150ml hexanaphthene is put into 500ml there-necked flask, at 65 ℃, treat that polyhutadiene dissolves completely, in system, slowly add 3.2 formic acid, 0.6g polyoxyethylene glycol, after dropwising, reflect again 0.5 hour, in 3.2g hydrogen peroxide is in 20min, be slowly added drop-wise in system, under constant temperature, continue reaction 2 hours, after reaction finishes, product is poured out, add dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain white toughness product.
By 15g polyhutadiene, 200ml hexanaphthene is put into 500ml there-necked flask, at 60 ℃, treat that polyhutadiene dissolves completely, in system, slowly add 3.2 formic acid, 0.6g polyoxyethylene glycol, after dropwising, reflect again 0.5 hour, in 3.2g hydrogen peroxide is in 20min, be slowly added drop-wise in system, under constant temperature, continue reaction 4 hours, after reaction finishes, product is poured out, add dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain white toughness product.
By 15g polyhutadiene, 200ml hexanaphthene is put into 500ml there-necked flask, at 70 ℃, treat that polyhutadiene dissolves completely, in system, slowly add 3.2 formic acid, 0.6g polyoxyethylene glycol, after dropwising, reflect again 0.5 hour, in 3.2g hydrogen peroxide is in 20min, be slowly added drop-wise in system, under constant temperature, continue reaction 1.5 hours, after reaction finishes, product is poured out, add dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain white toughness product.
Fig. 1, Fig. 2 are photo figure, the unintelligible the understanding of the present invention that do not affect of word in figure;
The structural analysis of epoxidized polybutadiene prepared by this method is as follows:
1. epoxidized polybutadiene infrared spectrogram as shown in Figure 1.
In Fig. 1, the oxirane ring stretching vibration absorption peak, 889 that 1242cm-1 place occurs, the hydrocarbon bond bending vibration absorption peak of oxirane ring that 818cm-1 occurs and 970cm-1 place belong to the disappearance of flexural vibration absorption peak of the hydrocarbon key of cis-Isosorbide-5-Nitrae structure pair keys; 915cm-11, weakening of 2-vinyl structure double key carbon hydrogen bond flexural vibration absorption peak, has all proved the existence of epoxide group in ESPB.
2. the H-NMR spectrum analysis of epoxidized polybutadiene
In Fig. 2, chemical shift is that the absorption peak at 2.833 and 2.897 places is the absorption peak of epoxy group(ing) proton, thereby has further confirmed to have epoxide group in product ESPB.
Claims (5)
1. an epoxidation 1, the preparation method of 2-polyhutadiene, is characterized in that, described method comprises following preparation process:
A, component A and B component are added in reaction flask, in 65 ℃ of lower magnetic forces, be stirred to component A and dissolve, in reaction flask, add component C and D, stir, in system, add quantitative component E, under constant temperature, react for some time, after reaction finishes, product is poured out, added dehydrated alcohol that solid is separated out, sedimentation for some time, suction filtration, by sodium hydrogen carbonate solution and distilled water difference washed product solid several times, put into 60 ℃ of vacuum-drying 12h of baking oven, obtain product.
2. a kind of epoxidation 1 according to claim 1, the preparation method of 2-polyhutadiene, is characterized in that, described component A is high molecular syndiotaxy 1,2-polyhutadiene, number-average molecular weight Mn is 1200000, degree of crystallinity 20%, 1,2-structural content is greater than 95%.
3. a kind of epoxidation 1 according to claim 1, the preparation method of 2-polyhutadiene, is characterized in that, described B component is lower paraffin hydrocarbons or naphthenic hydrocarbon, comprises hexanaphthene, normal hexane.
4. a kind of epoxidation 1 according to claim 1, the preparation method of 2-polyhutadiene, is characterized in that, and described component D is a kind of phase-transfer catalyst, and structure is (CH
2cH
2o)
n.
5. a kind of epoxidation 1 according to claim 1, the preparation method of 2-polyhutadiene, is characterized in that, the mass concentration of described component A is 8g/dL, the mass concentration ratio of component C and component A is Mc/Ma=21.5%, and the mol ratio of component C and component E is: C/E=1:1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262543A (en) * | 2014-09-09 | 2015-01-07 | 沈阳化工大学 | Method for preparing maleic anhydride-grafted 1,2-polybutadiene |
| CN105777950A (en) * | 2016-03-29 | 2016-07-20 | 沈阳化工大学 | Preparation method of silane-grafted modification ethylene-propylene-diene monomer rubber through solution method |
| CN107915797A (en) * | 2017-11-22 | 2018-04-17 | 山东玉皇化工有限公司 | Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof |
| CN108753217A (en) * | 2018-06-26 | 2018-11-06 | 西安近代化学研究所 | A kind of composite propellant lining |
| CN109135634A (en) * | 2018-07-27 | 2019-01-04 | 四川大学 | A method of preparing high thermal conductivity low-dielectric loss compound sticking film |
| CN113072652A (en) * | 2021-04-25 | 2021-07-06 | 岭南师范学院 | Quantitative epoxidized natural rubber and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262543A (en) * | 2014-09-09 | 2015-01-07 | 沈阳化工大学 | Method for preparing maleic anhydride-grafted 1,2-polybutadiene |
| CN105777950A (en) * | 2016-03-29 | 2016-07-20 | 沈阳化工大学 | Preparation method of silane-grafted modification ethylene-propylene-diene monomer rubber through solution method |
| CN107915797A (en) * | 2017-11-22 | 2018-04-17 | 山东玉皇化工有限公司 | Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof |
| CN107915797B (en) * | 2017-11-22 | 2019-12-31 | 山东玉皇化工有限公司 | Liquid polybutadiene rubber, epoxidized liquid polybutadiene rubber and preparation method thereof |
| CN108753217A (en) * | 2018-06-26 | 2018-11-06 | 西安近代化学研究所 | A kind of composite propellant lining |
| CN109135634A (en) * | 2018-07-27 | 2019-01-04 | 四川大学 | A method of preparing high thermal conductivity low-dielectric loss compound sticking film |
| CN109135634B (en) * | 2018-07-27 | 2020-08-25 | 四川大学 | Method for preparing high-thermal-conductivity low-dielectric-loss composite adhesive film |
| CN113072652A (en) * | 2021-04-25 | 2021-07-06 | 岭南师范学院 | Quantitative epoxidized natural rubber and preparation method thereof |
| CN113072652B (en) * | 2021-04-25 | 2022-06-28 | 岭南师范学院 | Quantitative epoxidized natural rubber and preparation method thereof |
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