CN104292372A - Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof - Google Patents
Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof Download PDFInfo
- Publication number
- CN104292372A CN104292372A CN201310304276.4A CN201310304276A CN104292372A CN 104292372 A CN104292372 A CN 104292372A CN 201310304276 A CN201310304276 A CN 201310304276A CN 104292372 A CN104292372 A CN 104292372A
- Authority
- CN
- China
- Prior art keywords
- epoxidation
- trans
- polydiolefin
- compounded rubber
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an epoxidation trans-1, 4-polydiolefin compound rubber and a preparation method thereof, and relates to the field of polymer materials. The epoxidation compound rubber contains 2-70 mol% of epoxy group. One of the preparation method is by dissolving trans-1,4-polydiolefin compound rubber in a solvent, and then slowly adding an organic acid for reaction under the action of stirring. A second preparation method is by dispersing the trans-1, 4-polydiolefin compound rubber in a water containing a surfactant, and performing an epoxidation reaction in a reactor with stirring by using an organic peracid as an epoxidation reagent. By controlling the reaction temperature, dosage of epoxidation reagent and reaction time, the epoxidation trans-1,4-polydiolefin rubber compound with certain epoxy group content is prepared. The introduction of epoxy groups increases the adhesive force with polar substances, wet skid resistance and air tightness, and can be used in conveyor belt, tyre rubber and damping material.
Description
Technical field
The invention belongs to polydiolefin field of rubber materials, in particular to trans 1, the epoxidation preparation method of 4-polydiolefin compounded rubber and the epoxidation trans Isosorbide-5-Nitrae-polydiolefin compounded rubber that can use in occasions such as tire, rubber overshoes, shock absorber parts obtained by this method.
Background technology
Epoxy natural rubber is the modified compound of a kind of natural rubber that natural rubber (NR) is prepared by epoxidation reaction.After epoxidation reaction, in natural rubber, original nonpolar carbon-to-carbon double bond is converted into epoxide group, thus substantially improve the performance such as anti-slippery, oil-proofness, against gas transmission perviousness, cohesiveness of natural rubber, can at occasion Some substitute butyronitrile such as doughnut, oil-resistant sealing element, bottle stopper, cord dippings, along fourth, isoprene-isobutylene rubber etc.Since (Pummer R. such as Pummer and Burkhard in 1922, Burkhard P. A., Uber kautschuk, Ber. Dtsch. Chem. Ges., 1922,55:3458-3472) adopt peroxy acid and natural rubber latex to react, after successfully having prepared epoxy natural rubber, the epoxidation modification of unsaturated polymer (polyhutadiene, polyisoprene, styrene-butadiene rubber(SBR) etc.) is widely studied.
Except natural rubber can adopt latex directly to carry out except epoxidation modification, the epoxidation modification of most of traditional unsaturated polymer adopts solution to carry out, the method needs to use a large amount of organic solvent, reaction terminates rear needs and reclaims a large amount of organic solvent, energy consumption and cost are all higher, and the use of a large amount of organic solvent simultaneously can cause environmental pollution etc. again.
In view of more than, Chinese invention patent Zl 00123985.6 report adopt water phase suspension prepare epoxidation trans-Isosorbide-5-Nitrae-polyisoprene, overcome the shortcoming of above-mentioned emulsion method and solution method epoxidation modification.Due to water phase suspension and Powdered anti-form-1, the feature of 4-polyisoprene, prepared epoxidation trans-1,4-polyisoprene is multi-phase multi-component state, make it with anti-form-1,4-polyisoprene itself lower rolling resistance and heat-dissipating, simultaneously due to the introducing of polar loop oxygen groups, possessed the anti-slippery improved, binding property and polarity.
Chinese invention patent ZL 200910174494.4 reports a kind ofly has that less rolling resistance, heat-dissipating are low, the novel anti-form-1 of excellent in fatigue, 4-polydiolefin compounded rubber and preparation method thereof.This anti-form-1,4-polydiolefin compounded rubber may be used for the field such as tire, cushioning material.Non-polar rubber material and polar material is all related in a lot of Application Areass of current rubber, as the bonding of steel wire, nylon, magnet, copper cash etc., and the anti-form-1 of this patent report, 4-polydiolefin compounded rubber is also a kind of non-polar polymer, and this just limits its Application Areas and result of use to a certain extent.
If by simple polymer modification method, make nonpolar rubber have polarity, the binding property of itself and polar material will be increased.
Summary of the invention
An object of the present invention is for current nonpolar trans 1, between 4-polydiolefin compounded rubber and polar material, binding property is weak and trans 1, there is the shortcoming of anti-slippery difference in 4-polydiolefin compounded rubber, reacted by epoxidation modification, prepare epoxidation trans 1,4-polydiolefin compounded rubber, provides a kind of novel polarity trans elastomeric material.
Two of object of the present invention is just to provide the preparation method of epoxidation trans Isosorbide-5-Nitrae-polydiolefin compounded rubber.
The preparation method of epoxidation trans polydiolefin compounded rubber of the present invention adopts epoxidation reagent to carry out epoxidation reaction modification to trans polydiolefin compounded rubber.Two kinds of methods can be adopted to carry out: a kind of method is dissolved in suitable solvent by trans polydiolefin compounded rubber, then epoxidation reagent be joined in above-mentioned solution and react, obtained epoxidation trans polydiolefin compounded rubber; Or adopt alternatively, be: under the effect of stirring, make trans polydiolefin compounded rubber Granular composite in water, then epoxidation reagent is joined in above-mentioned dispersion system, obtained epoxidation trans polydiolefin compounded rubber.Prepared epoxidation trans polydiolefin compounded rubber, different according to its preparation method, can be block or particulate state.
Epoxidation trans polydiolefin compounded rubber prepared by preparation method one of the present invention, owing to have employed solution method epoxidation modification, the distribution uniform of epoxide group in compounded rubber molecular chain; Meanwhile, each different components in compounded rubber all has identical probability to be at least partially epoxidized modification.
Epoxidation trans polydiolefin compounded rubber prepared by preparation method two of the present invention, carry out epoxidation modification owing to have employed two-phase dispersion method, the degree that epoxidation reaction is carried out at polymer surfaces will be far longer than the degree of carrying out at polymeric inner.The epoxidation trans polydiolefin compounded rubber of such preparation, because epoxide group is at the inside and outside skewness of particle, good binding property, anti-slippery, barrier and stopping property that the original excellent properties of compounded rubber and epoxidation are given therefore can be had concurrently.
Epoxidation trans polydiolefin compounded rubber of the present invention, the epoxide group molar content that the nuclear-magnetism method of this epoxidation compounded rubber measures is 2 mol% ~ 70 mol%, residual double bonds molar content is 30 mol ~ 98 mol%, and the distribution of epoxide group in compounded rubber is random and/or block.The content of regulating ring oxygen groups in compounded rubber can be carried out by preparation method, charging capacity, reaction times and temperature of reaction, and then obtain the adjustable epoxidation trans polydiolefin compounded rubber of stuctures and properties.
The concrete steps of epoxidation trans polydiolefin compounded rubber preparation method one of the present invention are as follows:
Quantitative solvent and trans polydiolefin compounded rubber is added in reaction unit, under the effect of stirring, make this compounded rubber dissolve form uniform solution, then by epoxidation reagent according to being 0.1 ~ 1.3 join in above-mentioned solution with the mol ratio of double bond in trans polydiolefin compounded rubber, regulation system pH value is acid, and temperature of reaction is 0 ~ 80
oc, reaction times is 0.1 ~ 10 hour, after reaction specified time, stopped reaction, pours into reaction solution in hot water, under stirring, recycling design also makes polymer fibrids, then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also with distilled water cleaning to neutral, obtained block epoxidation trans polydiolefin compounded rubber after drying.Epoxide group in the present invention is random distribution in compounded rubber molecular chain.
The concrete steps of epoxidation trans polydiolefin compounded rubber preparation method two of the present invention are as follows:
Quantitative water, tensio-active agent and trans polydiolefin compounded rubber is added in reaction unit, under the effect of stirring, this compounded rubber is dispersed in water, then by epoxidation reagent according to being 0.1 ~ 1.3 join in above-mentioned solution with the mol ratio of double bond in trans polydiolefin compounded rubber, regulation system pH value is acid, and temperature of reaction is 0 ~ 80
oc, reaction times is 0.1 ~ 10 hour, after reaction specified time, stopped reaction, then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also with distilled water cleaning to neutral, is still kept the epoxidation trans polydiolefin compounded rubber of using trans-polyisoprene compounded rubber initial configuration after drying.Epoxide group integrated distribution in the present invention is at compounded rubber particle surface.
Described solvent is that one or more in chloroform, benzene, toluene, tetracol phenixin, p-Xylol, heptane, hexanaphthene, normal hexane, tetrahydrofuran (THF), ethyl acetate are composite, preferred toluene and chloroform.
Described epoxidation reagent is one or more in Peracetic Acid, peroxyformic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, preferred Peracetic Acid and peroxyformic acid.Preferred peroxyformic acid can adopt formic acid acid and hydrogen peroxide to generate at reaction system situ, and preferred Peracetic Acid is that acetic acid and hydrogen peroxide are pre-configured to certain density peracetic acid soln.
The epoxide group molar content of the epoxidation trans polydiolefin compounded rubber that the consumption of described epoxidation reagent is prepared as required is determined.
Described tensio-active agent is that one or more in sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, PDDA, stearic acid, quaternary ammonium compound, alkylphenol polyoxyethylene, sorbitan ester are composite, and preferred tensio-active agent is sodium lauryl sulphate.The weight ratio of tensio-active agent and trans compounded rubber is 0.5 ~ 10:100.
Epoxidation trans polydiolefin compounded rubber prepared by the present invention, compared with conventional rubber, has possessed high warping strength fatigability, binding property, anti-slippery and resistance to air loss simultaneously, can meet different rubber applications occasions when being used alone.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Unless stated otherwise, the method and apparatus that the present invention adopts is ordinary method and the equipment of this area.
The test condition of covering polymer is as follows:
1H-NMR: adopt German BrukerFT/AC-80 type nmr determination, test sample deuterochloroform makes the solution of about 5%.In the 1H-NMR spectrogram of ETPI, be that 2.71ppm place occurs adding significantly because of epoxidation group the methyne resonance peak caused in chemical shift, 5.11ppm place is olefinic protons absorption peak, by recording peak area (A) ring oxygen groups molar content (E%) at peak, 2.71ppm and 5.11ppm two place:
E%?=?[A2.71/(A2.71+A5.11)]?*100%
Embodiment 1
The there-necked flask of 5000mL is cleaned and dries, add the distilled water of 5g Sodium dodecylbenzene sulfonate and 2000ml, start after stirring makes Sodium dodecylbenzene sulfonate dissolve completely and add trans polydiolefin compounded rubber particle 300g, under the effect of stirring, make it disperse, the ratio being 0.8 according to the mol ratio of organic peracid and compounded rubber double bond adds pre-configured organic peroxy acetic acid, regulation system pH value is 5, and hierarchy of control temperature is 50 degree, reacts 8 hours.After dilute solution of sodium hydroxide neutralization reaction system to neutrality, suction filtration also cleans 3 times with distilled water, weighs after drying.Gained epoxidation trans polydiolefin compounded rubber is 350g, and calculating its epoxide group molar content through nuclear-magnetism method is 68.5%.
Embodiment 2
Synthetic method is with embodiment 1, and just the mol ratio of organic peracid and compounded rubber double bond is 0.35.Gained epoxidation trans polydiolefin compounded rubber is 346g, and calculating its epoxide group molar content through nuclear-magnetism method is 33.8%.
Embodiment 3
The reactor of 50L is cleaned, add the distilled water of 40g Sodium dodecylbenzene sulfonate and 20000mL, start after stirring makes Sodium dodecylbenzene sulfonate dissolve completely and add trans polydiolefin compounded rubber 5000g, under the effect of stirring, make it disperse, the ratio being 0.6 according to the mol ratio of organic peracid and compounded rubber double bond adds pre-configured organic peroxy acetic acid, regulation system pH value is 5, and hierarchy of control temperature is 60 degree, reacts 6 hours.After dilute solution of sodium hydroxide neutralization reaction system to neutrality, suction filtration also cleans 3 times with distilled water, weighs after drying.Gained epoxidation trans polydiolefin compounded rubber is 5430g, and calculating its epoxide group molar content through nuclear-magnetism method is 50.6%.
Embodiment 4
The reactor of 50L is cleaned, add the toluene of 20000mL and the trans polydiolefin compounded rubber of 2000g, be warming up to 40 degree and start stirring and make polymer dissolution, the ratio being 0.4 according to the mol ratio of organic peracid and compounded rubber double bond adds pre-configured organic peroxy acetic acid, regulation system pH value is 5, hierarchy of control temperature is 40 degree, reacts 6 hours.Pour in boiling water by whole system after stopped reaction, recycling design also makes polymer fibrids.Then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also cleans 3 times with distilled water, weighs after drying.Gained epoxidation trans polydiolefin compounded rubber is 2250g, and calculating its epoxide group molar content through nuclear-magnetism method is 40.0%.After polymkeric substance is mixing, make cross-linked rubber and carry out bounding force test, obtaining its cord extraction power is 1500N, higher than the 220N of trans Isosorbide-5-Nitrae-polydiolefin compounded rubber 7 times.The rebound value of epoxidation trans polydiolefin compounded rubber 20 degree is lower by 60% than trans polydiolefin compounded rubber, illustrates that its anti-slippery improves greatly.
Embodiment 5
The there-necked flask of 5000mL is cleaned and dries, add the toluene of 2000mL and the trans polydiolefin compounded rubber of 200g, be warming up to 40 degree and start stirring and make polymer dissolution, the ratio being 0.5 according to the mol ratio of organic peracid and compounded rubber double bond adds pre-configured organic peroxy acetic acid, regulation system pH value is 5, hierarchy of control temperature is 40 degree, reacts 4 hours.After stopped reaction, whole system is poured in boiling water, recycling design.Then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also cleans 3 times with distilled water, weighs after drying.Gained epoxidation trans polydiolefin compounded rubber is 230g, and calculating its epoxide group molar content through nuclear-magnetism method is 49.5%.
Claims (8)
1. epoxidation trans Isosorbide-5-Nitrae-polydiolefin compounded rubber, is characterized in that, the epoxide group molar content of this epoxidation compounded rubber is 2 mol% ~ 70 mol%, and residual double bonds molar content is 30 mol ~ 98 mol%.
2. the preparation method one of epoxidation compounded rubber according to claim 1, synthesize according to the following steps, it is characterized in that: in reaction unit, add quantitative solvent and trans 1,4-polydiolefin compounded rubber, under the effect of stirring, make this compounded rubber dissolve form uniform solution, then be 0.1 ~ 1.3 join in above-mentioned solution by epoxidation reagent according to the mol ratio with trans polydiolefin compounded rubber double bond, regulation system pH value is acid, and temperature of reaction is 0 ~ 80
oc, reaction times is 0.1 ~ 10 hour, after reaction specified time, stopped reaction, pours into reaction solution in hot water, under stirring, recycling design also makes polymer fibrids, then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also with distilled water cleaning to neutral, obtained block epoxidation trans polydiolefin compounded rubber after drying.
3. the preparation method two of epoxidation compounded rubber according to claim 1, synthesize according to the following steps, it is characterized in that: in reaction unit, add quantitative water, tensio-active agent and trans polydiolefin compounded rubber, under the effect of stirring, this compounded rubber is dispersed in water, then by epoxidation reagent according to being 0.1 ~ 1.3 join in above-mentioned solution with the mol ratio of double bond in trans polydiolefin compounded rubber, regulation system pH value is acid, and temperature of reaction is 0 ~ 80
oc, reaction times is 0.1 ~ 10 hour, after reaction specified time, stopped reaction, then to use in dilute solution of sodium hydroxide and after polymer slurries to neutrality, suction filtration also with distilled water cleaning to neutral, is still kept the epoxidation trans polydiolefin compounded rubber of using trans-polyisoprene compounded rubber initial configuration after drying.
4. preparation method according to Claims 2 or 3, is characterized in that: described epoxidation reagent is one or more in Peracetic Acid, peroxyformic acid, benzoyl hydroperoxide, metachloroperbenzoic acid, preferred Peracetic Acid and peroxyformic acid.
5. Peracetic Acid according to claim 4 adopts Glacial acetic acid, hydrogen peroxide and the vitriol oil proportionally to mix, and at room temperature display use after 24 hours; Described peroxyformic acid adopts formic acid and hydrogen peroxide in reaction system, drip in-situ synthesized simultaneously and obtains.
6. the preparation method of epoxidation trans polydiolefin compounded rubber according to claim 2, is characterized in that described solvent is that one or more in chloroform, benzene, toluene, tetracol phenixin, p-Xylol, heptane, hexanaphthene, normal hexane, tetrahydrofuran (THF), ethyl acetate are composite.
7. the preparation method of epoxidation trans polydiolefin compounded rubber according to claim 3, is characterized in that described tensio-active agent is that one or more in sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, PDDA, stearic acid, quaternary ammonium compound, alkylphenol polyoxyethylene, sorbitan ester are composite; The weight ratio of tensio-active agent and trans compounded rubber is 0.5 ~ 10:100.
8. epoxidation trans polydiolefin compounded rubber according to claim 1 has excellent anti-slippery and binding property, can be used for tire, rubber overshoes, shock absorber part and oil-resistant seal material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310304276.4A CN104292372A (en) | 2013-07-19 | 2013-07-19 | Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310304276.4A CN104292372A (en) | 2013-07-19 | 2013-07-19 | Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104292372A true CN104292372A (en) | 2015-01-21 |
Family
ID=52312345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310304276.4A Pending CN104292372A (en) | 2013-07-19 | 2013-07-19 | Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104292372A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818818A (en) * | 2019-11-22 | 2020-02-21 | 湖南大学 | Environment-friendly synthesis method of epoxidized gutta percha, epoxy anticorrosive paint and preparation method |
| CN113336877A (en) * | 2021-06-09 | 2021-09-03 | 北京化工大学 | Preparation method of epoxidized butyl rubber |
-
2013
- 2013-07-19 CN CN201310304276.4A patent/CN104292372A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 张萌萌等: "环氧化反式-1,4-聚异戊二烯的合成与表征", 《化学世界》 * |
| 胡婧等: "用溶液法环氧化改性反式-1,4-聚异戊二烯及产物表征", 《合成橡胶工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818818A (en) * | 2019-11-22 | 2020-02-21 | 湖南大学 | Environment-friendly synthesis method of epoxidized gutta percha, epoxy anticorrosive paint and preparation method |
| CN113336877A (en) * | 2021-06-09 | 2021-09-03 | 北京化工大学 | Preparation method of epoxidized butyl rubber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107236437B (en) | A kind of water-based anticorrosive paint and preparation method thereof | |
| CN103087607B (en) | Single-component curable waterborne epoxy insulating paint and preparation method of waterborne epoxy insulating paint | |
| CN103910816B (en) | The epoxidation trans polyisoprene rubber preparation method of a kind of improvement | |
| CN104371537B (en) | Anticorrosive paint and preparation method thereof | |
| CN101955716B (en) | Zinc-rich steel structure anti-corrosion primer based on epoxy resin and preparation method thereof | |
| CN110016289A (en) | A kind of high performance polymer modified bitumen water-repellent paint and preparation method thereof | |
| JP2015078280A5 (en) | Method for manufacturing vehicle member | |
| CN103965823B (en) | A kind of nitroso-fluoro-elastomers tackiness agent and preparation technology thereof | |
| CN103159963B (en) | Preparation method of powdered acrylonitrile-butadiene rubber with high performance | |
| CN104292372A (en) | Epoxidation of trans-1, 4-polydiolefin compound rubber and preparation method thereof | |
| CN104388095A (en) | Double-component nano high-polymer sand stabilization material and sand stabilization method thereof | |
| CN114231228B (en) | Magnetorheological repairing material, preparation method thereof and oil pipeline repairing method | |
| CN109385181A (en) | A kind of preparation method containing epoxidation gutta percha coating | |
| CN111992151A (en) | preparation method of pH stimulation responsive slow-release hybrid microspheres | |
| CN103642422A (en) | Reparative conductive adhesive and preparation method thereof | |
| CN105400238B (en) | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste | |
| CN110734587B (en) | Method for preparing nitrile rubber from modified carbon black | |
| CN105331054A (en) | Composite conductive film | |
| CN104497211A (en) | Efficient concrete thickener and preparation method thereof | |
| CN101857711B (en) | Method for preparing thermoplastic resin | |
| CN110734594B (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon black | |
| CN105802286A (en) | Preparation method of emulsion type waterproof agent containing mixed solvent and used for fiber board | |
| CN103539948B (en) | A kind of preparation method of high-tenacity adhesion type powdered polychloroprene rubber | |
| CN103539949B (en) | A kind of preparation method of high-performance liquid styrene butadiene rubber | |
| CN102942698B (en) | Preparation method of core-shell polymer nanoparticles with controllable shell thickness |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150121 |