CN101942043A - Method for preparing epoxidized natural rubber - Google Patents
Method for preparing epoxidized natural rubber Download PDFInfo
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- CN101942043A CN101942043A CN2010102932731A CN201010293273A CN101942043A CN 101942043 A CN101942043 A CN 101942043A CN 2010102932731 A CN2010102932731 A CN 2010102932731A CN 201010293273 A CN201010293273 A CN 201010293273A CN 101942043 A CN101942043 A CN 101942043A
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Abstract
The invention discloses a method for preparing epoxidized natural rubber, which comprises the following steps of: diluting 100 parts of condensed natural rubber latex with the total solid content of 60 percent with deionized water until the total solid content is 30 percent, adding 1 to 3 parts of 20 percent polyoxyethylene lauryl ether with stirring, stabilizing the mixed solution for 2 hours, slowly adding 16 to 24 parts of 86 percent formic acid and 35 to 45 parts of 30 percent hydrogen peroxide, finishing reaction at certain reaction temperature, for a certain reaction time and in an ultrasonic treatment way, adjusting a pH value to 8 to 9 with ammonia water, and performing coagulation, dehydration, rinsing, granulation and drying to prepare the epoxidized natural rubber with the epoxidization degree of 10 to 50 percent, the ring-opening substance content of less than 3.0 percent, relatively higher quality consistency and capability of satisfying needs in application performance.
Description
Technical field
The present invention relates to the method that a kind of ultrasonic wave intensifier ring oxidizing reaction prepares epoxy natural rubber.
Background technology
The structural unit of natural rubber (NR) is cis-1, and 4 one isoprene have a hydrogen atom by methyl substituted on the double-linked carbon, causes the cloud density of two keys to increase, and is easy to take place the cationoid reaction with peroxy acid.The two keys of part on the NR molecular chain prepare epoxy natural rubber (ENR) through the epoxidation chemical modification, structure and the performance characteristics of NR had both been remained with, can divide compatible and covulcanization with non-polar rubber generating units such as NR, SBR, BR, have the certain polarity and the reactivity of epoxide group again, help improving the gripping power (anti-slippery) of rubber to wet road surface, and can produce stronger dipole, hydrogen bond even covalent linkage effect with inorganic filler surface, combine with the interface of filler thereby improve rubber.The effect of this two aspect can cause tire with the conventional mechanical property of non-polar rubber matrix material and the improvement of dynamic property, comprises the reduction of rolling resistance, the raising of anti-slippery and the improvement of wear resistance etc.And in the preparation process of ENR, in the time of NR molecular chain initial ring oxidizing reaction, having the secondary open loop side reaction of epoxide group, open-loop products produces a lot of adverse influences to the performance of ENR.Therefore, accurately control the epoxidation level of ENR, suppress the generation of secondary open-loop products, become research emphasis in recent years.
In theory, under acidic conditions, adopt superoxide can both make unsaturated carbon-to-carbon double bond epoxidation under employing peroxy acid or the alkaline condition.But carrying out epoxidation reaction for the such aqueous dispersion of NR needs to consider from several respects: 1. reaction system must be fit to water medium and have certain stability; 2. speed of reaction and reaction severe degree are moderate, and temperature of reaction is easy to control; 3. the reaction system by product is less, and can too much influence not arranged to the application performance of principal product; 4. reaction easily stops, and principal product separates, aftertreatment is more convenient, and residual reactant does not have too much influence to the performance of principal product.Based on above reason, mainly adopt at present and under acidic conditions, NR is carried out epoxidation and prepare ENR with Peracetic Acid or peroxyformic acid.
The epoxidation of natural rubber can carry out in solution and latex system respectively, and solution method is dried glue to be dissolved in to be made into certain density solution in the organic solvent earlier, carries out epoxidation reaction then.Emulsion method (Gelling I.R., Modification ofnatural rubber latex with peracetic acid.Rubber Chemistry and Technology 1985,58 (1), 86-97; Heping, Y.; Sidong, L.; Zheng, P., Preparation and study of epoxidized naturalrubber.Journal of Thermal Analysis and Calorimetry 1999,58, (2), 293-299) then directly react in the latex system, add epoxidation reagent and react.Concerning natural rubber, in solution, carry out process for epoxidation and be not suitable for and commercially produce, because prepare suitable natural rubber solution and reclaim the expense of modified rubber from solution big, industry is complicated.Therefore, directly epoxidation has caused people's bigger interest in latex, and its epoxidation reagent adopts peroxy acid usually.
Be in the reaction system of epoxidation reagent with the peroxy acid, existing the competing reaction of epoxidation reaction and the open loop of acid catalysis epoxide group.Nearly all research institution all adopts high acidity, high-temperature reaction conditions to prepare epoxy natural rubber both at home and abroad.Acidity is big more, and temperature is high more, and speed of reaction is fast more, and the easy more generation of secondary open loop side reaction of epoxide group must have a strong impact on the quality and the quality conformance of product.By the consumption of suitable adjusting peroxy acid and the temperature of reaction of system, can lower the generation of open loop side reaction, but this method is to reduce epoxidation reaction speed and epipodium oxidisability is a cost.
C.M.Lau follows the tracks of the variation in the epoxidation process of natural rubber latex particle with Electronic Speculum, found to occur after the oxidation of natural rubber particle initial ring a kind of " besieged " structure (C.M.Lau of feature, J.B.Gomez, and A.Subramanium, Proc.Int.Rubb.Conf., Kuala Lumpur, Malaysia, 1985,2,524).Epoxidation latex is made up of the rubber particles of a series of different rings degree of oxidations, and the epoxy natural rubber of preparation has ununiformity.This also is the basic reason that epoxy natural rubber can't reach quality conformance.
Therefore, also need to provide a kind of quality of epoxy natural rubber that can make to reach conforming preparation method.
Summary of the invention
The object of the present invention is to provide the preparation method of the natural rubber of a kind of epoxidation, this method can make the quality of epoxy natural rubber reach consistence, satisfies the needs of epoxy natural rubber application performance.
Specifically, the present invention is in the system of natural rubber latex, formic acid and hydrogen peroxide, adopt the technology of ultrasonic wave intensifier ring oxidizing reaction, with the ultrasonic wave of 20KHz reaction system is carried out the supersound process of regular hour every the regular hour, after reaction finishes, carry out conventional processing again, solidify, granulation, drying, make epoxidation level and be 10%～50%, ring-opening product content less than 3%, quality conformance is better, can satisfy the epoxy natural rubber of application performance needs.
Specific embodiments of the present invention is as follows:
With 100 parts of total solids levels is that 60% concentrated natural latex is diluted to 30% with deionized water, add 1～3 part of concentration while stirring and be 20% polyoxyethylene lauric acid ether, after stablizing 2 hours, slowly add 16～24 parts of concentration and be 86% formic acid and 35～45 parts of concentration and be 30% hydrogen peroxide, in the certain reaction temperature, the mode that reaction times and ultrasonic echography are handled is finished down to reaction, regulate pH value to 8～9 with ammoniacal liquor subsequently, solidify, dehydration, rinsing, granulation, dry, making epoxidation level is 10%～50%, the epoxy natural rubber of ring-opening product content＜3.0%.
The preparation method of epoxy natural rubber of the present invention is characterized in that the mode that described ultrasonic echography is handled is every interval 50 minutes, and to system supersound process 10～20 minutes, hyperacoustic ultrasonic frequency was 20KHz, and ultrasonic power is 50W.
Epoxy natural rubber of the present invention the preparation method, it is characterized in that described is that temperature of reaction is to be 30 ℃～50 ℃, the reaction times is 6～30 hours.
Key problem in technology point of the present invention
Key problem in technology point of the present invention is: the technology that adopts ultrasonic wave intensifier ring oxidizing reaction, on the one hand, ultrasonic wave can be accelerated the skin motion to the natural rubber particle of molecular chain that natural rubber particle internal layer is wrapped, make it and epoxidation reagent initial ring oxidizing reaction, reach the even epoxidised purpose of intensifier ring rate of oxidation and natural rubber molecular chain; Another side; ultrasonic wave can be accelerated the rubber particles skin internal layer motion of epoxidised molecular chain to particle taken place; be in the state of being wrapped; make it with system in isolated the coming of epoxidation reagent; thereby can effectively suppress epoxide group in the open loop of preparation feedback stage, guarantee the quality product and the quality conformance of epoxy natural rubber.
The inventive method has following significant effect:
---adopt the technology of ultrasonic wave intensifier ring oxidizing reaction, have the natural rubber of acceleration epoxidation reaction speed, even epoxy natural rubber molecular chain and suppress epoxide group in advantages such as preparatory phase generation secondary open loop side reactions.
---adopt the present invention to prepare epoxy natural rubber and surplus and equality people (Heping, Y.; Sidong, L.; Zheng, P., Preparation and study of epoxidized natural rubber.Journal of Thermal Analysis andCalorimetry 1999,58, (2), preparation method 293-299) compares, behind the epoxidation reaction 12h, the ENR epoxidation level exceeds 3.9%, and open-loop products content reduces 1.0%; Behind the reaction 24h, epoxidation level exceeds 12.2%, and open-loop products content reduces 1.1%.
Therefore, adopt the present invention to prepare epoxy natural rubber, epoxidation reaction can be carried out under more gentle low sour condition, can realize the accurate control of the epoxidation degree of epoxy natural rubber, the epoxy natural rubber of obtained performance excellence; Can effectively suppress epoxide group again in the open loop of preparation feedback stage, guarantee the quality product and the quality conformance of epoxy natural rubber.
Description of drawings
Fig. 1 is the influence contrast figure of ultrasonication to the ENR epoxidation level, be described in temperature of reaction and be under 50 ℃ the condition, adopt the inventive method to prepare ENR, and be in the same old way with the ENR of preparation method's preparation of surplus and equality people, the investigation ultrasonication is to the influence of ENR epoxidation level.As can be seen from the figure, in the identical reaction times, adopt the epoxidation level of the ENR of the inventive method preparation all to be higher than the epoxidation level of ENR of preparation method's preparation of surplus and equality people, illustrate that the inventive method can effectively quicken the epoxidation reaction speed of natural rubber.
Fig. 2 is the influence contrast figure of ultrasonication to ENR ring-opening product content, be described in temperature of reaction and be under 50 ℃ the condition, adopt preparation method of the present invention to prepare epoxy natural rubber, and be in the same old way with the epoxy natural rubber of preparation method's preparation of surplus and equality people, ultrasonication is to the influence of epoxy natural rubber ring-opening product content.As can be seen from the figure; in the identical reaction times; the open loop oxygen level of the ENR of employing the inventive method preparation all is lower than the ring-opening product content of the ENR of preparation method's preparation of adopting surplus and equality people; illustrate that the inventive method can effectively suppress epoxide group in the open loop of preparation feedback stage, guarantees the quality product and the quality conformance of epoxy natural rubber.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Except as otherwise noted, the umber that hereinafter adopts is dry weight part.
Embodiment 1:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 3 parts of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 21.6 parts of concentration then successively and be 86% formic acid, 43.2 parts of concentration is 30% hydrogen peroxide, and reaction is 6 hours under 50 ℃ of water bath condition, handles 10min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 12.6%, and ring-opening product content is 0.4%, and double bond content is 87%.
Embodiment 2:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 3 parts of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 21.6 parts of concentration then successively and be 86% formic acid, 43.2 parts of concentration is 30% hydrogen peroxide.Reaction is 12 hours under 50 ℃ of water bath condition, handles 10min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 32.5%, and ring-opening product content is 1.2%, and double bond content is 65.5%.
Embodiment 3:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 3 parts of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 21.6 parts of concentration then successively and be 86% formic acid, 43.2 parts of concentration is 30% hydrogen peroxide.Reaction is 24 hours under 50 ℃ of water bath condition, handles 10min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 49.5%, and ring-opening product content is 2.8%, and double bond content is 48.7%.
Embodiment 4:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 1 part of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 15 parts of concentration then successively and be 86% formic acid, 45 parts of concentration is 30% hydrogen peroxide.Reaction is 12 hours under 30 ℃ of water bath condition, handles 15min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 28.2%, and ring-opening product content is 1.3%, and double bond content is 69.9%.
Embodiment 5:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 1 part of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 16 parts of concentration then successively and be 86% formic acid, 45 parts of concentration is 30% hydrogen peroxide.Reaction is 30 hours under 30 ℃ of water bath condition, handles 20min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 43.5%, and ring-opening product content is 2.1%, and double bond content is 52.9%.
Embodiment 6:
Take by weighing 100 parts of total solids levels and be 60% concentrated natural latex,, add 2 parts of concentration and be 20% polyoxyethylene lauric acid ether with the concentration dilution to 30% of deionized water with concentrated natural latex, make latex keep stablizing 2 hours after.Under agitation add 24 parts of concentration then successively and be 86% formic acid, 40 parts of concentration is 30% hydrogen peroxide.Reaction is 18 hours under 40 ℃ of water bath condition, handles 20min every 50min with the ultrasonic echography of 20KHz.After reaction finishes, make temperature reduce to room temperature, add ammoniacal liquor the pH value of latex is adjusted to 9, adding alcohol solidification, dehydration, rinsing, granulation, drying with cooling bath.The epoxidation level of prepared epoxy natural rubber is 46.5%, and ring-opening product content is 2.8%, and double bond content is 49.8%.
Claims (3)
1. the preparation method of an epoxy natural rubber, it is characterized in that with 100 parts of total solids levels being that 60% concentrated natural latex is diluted to 30% with deionized water, add 1～3 part of concentration while stirring and be 20% polyoxyethylene lauric acid ether, after stablizing 2 hours, slowly add 16～24 parts of concentration and be 86% formic acid and 35～45 parts of concentration and be 30% hydrogen peroxide, in the certain reaction temperature, the mode that reaction times and ultrasonic echography are handled is finished down to reaction, regulate pH value to 8～9 with ammoniacal liquor subsequently, solidify, dehydration, rinsing, granulation, dry, making epoxidation level is 10%～50%, the epoxy natural rubber of ring-opening product content＜3.0%.
2. the preparation method of epoxy natural rubber according to claim 1, it is characterized in that the mode that described ultrasonic echography is handled is every interval 50 minutes, to system supersound process 10～20 minutes, hyperacoustic ultrasonic frequency was 20KHz, and ultrasonic power is 50W.
Epoxy natural rubber according to claim 1 the preparation method, it is characterized in that described is that temperature of reaction is to be 30 ℃～50 ℃, the reaction times is 6～30 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160514A (en) * | 2011-02-21 | 2011-08-24 | 中国热带农业科学院农产品加工研究所 | Method for promoting rubber tapping output of rubber tree using ultrasonic wave |
| CN104125966A (en) * | 2012-03-08 | 2014-10-29 | 住友橡胶工业株式会社 | Method for producing epoxidized natural rubber, rubber composition for tires, and pneumatic tire |
| CN104854177A (en) * | 2012-12-13 | 2015-08-19 | 朗盛丁基私人有限公司 | Processes for preparing epoxidized polymers |
| CN105859917A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of epoxidized emulsion polymerization rubber |
| CN105860175A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of tread rubber containing epoxidized styrene-butadiene rubber |
| CN107955087A (en) * | 2017-12-12 | 2018-04-24 | 中国热带农业科学院农产品加工研究所 | A kind of epoxy natural rubber and preparation method thereof |
| CN110684132A (en) * | 2019-09-12 | 2020-01-14 | 中国热带农业科学院橡胶研究所 | Oxidation-type constant-viscosity agent, constant-viscosity natural rubber product and preparation method thereof |
| CN111574643A (en) * | 2020-06-18 | 2020-08-25 | 中国热带农业科学院农产品加工研究所 | Method for improving damping temperature range of natural rubber and rubber |
| 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 (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160514B (en) * | 2011-02-21 | 2012-08-22 | 中国热带农业科学院农产品加工研究所 | Method for promoting rubber tapping output of rubber tree using ultrasonic wave |
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| US9567407B2 (en) | 2012-03-08 | 2017-02-14 | Sumitomo Rubber Industries, Ltd. | Method for producing epoxidized natural rubber, rubber composition for tires, and pneumatic tire |
| CN104125966A (en) * | 2012-03-08 | 2014-10-29 | 住友橡胶工业株式会社 | Method for producing epoxidized natural rubber, rubber composition for tires, and pneumatic tire |
| CN104854177A (en) * | 2012-12-13 | 2015-08-19 | 朗盛丁基私人有限公司 | Processes for preparing epoxidized polymers |
| CN105860175A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of tread rubber containing epoxidized styrene-butadiene rubber |
| CN105859917A (en) * | 2015-01-23 | 2016-08-17 | 中国石油天然气股份有限公司 | Preparation method of epoxidized emulsion polymerization rubber |
| CN107955087A (en) * | 2017-12-12 | 2018-04-24 | 中国热带农业科学院农产品加工研究所 | A kind of epoxy natural rubber and preparation method thereof |
| CN107955087B (en) * | 2017-12-12 | 2020-04-17 | 中国热带农业科学院农产品加工研究所 | Epoxidized natural rubber and preparation method thereof |
| CN110684132A (en) * | 2019-09-12 | 2020-01-14 | 中国热带农业科学院橡胶研究所 | Oxidation-type constant-viscosity agent, constant-viscosity natural rubber product and preparation method thereof |
| CN111574643A (en) * | 2020-06-18 | 2020-08-25 | 中国热带农业科学院农产品加工研究所 | Method for improving damping temperature range of natural rubber and rubber |
| 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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Application publication date: 20110112 |