CN1263902A - Process for preparing epoxidized elastomer - Google Patents
Process for preparing epoxidized elastomer Download PDFInfo
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- CN1263902A CN1263902A CN 00114939 CN00114939A CN1263902A CN 1263902 A CN1263902 A CN 1263902A CN 00114939 CN00114939 CN 00114939 CN 00114939 A CN00114939 A CN 00114939A CN 1263902 A CN1263902 A CN 1263902A
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- elastomerics
- superoxide
- rubber
- benzoyl hydroperoxide
- elastomer
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Abstract
A process for preparing epoxidized elastomer features that direct reaction of the elastomer containing residual double-bond on peroxide in reactor. Its advantages are gentle reaction condition, no solvent and pollution and integration of reaction with shaping.
Description
The present invention relates to elastomeric a kind of chemical modification method, particularly adopt reactive working method to prepare the epoxidation elastomerics.
As everyone knows, most of elastomerics is nonpolar, can cause them and other material adhesive and compatibility poor, thereby limit its range of application.Utilize two keys residual in the elastomerics, in conjunction with two these classical organic chemical reactionses of key addition reaction, in elastomer molecules, introduced reactive functional group (being generally polar group), not only can increase elastomeric polarity, and created condition for elastomeric secondary chemical modification.Elastomeric epoxidation modification is exactly one of them important content.It adopts peroxy acid usually, is epoxidation reagent as peroxyformic acid, Peracetic Acid, benzoyl hydroperoxide etc., and two keys are carried out electrophilic addition, obtains having the elastomerics of epoxy group(ing).As U.S. Pat P2, reported that polybutadiene elastomer carries out epoxidised process with benzoyl hydroperoxide in 842,513 in solution.U.S. Pat P3,022,322, USP3,555,112, also reported with aliphatics peroxy acid (as peracetic acid) and generated in-situ peroxyformic acid, peracetic acid among USP 4 528340 and the clear 49-476983 of Japanese publication and come epoxidized polybutadiene.U.S. Pat P4 has reported in solution system in 131,725, directly uses generated in-situ peroxyformic acid epoxidized thermoplastic elastomerics (SBS).English Patent BP2,113,692 have reported with peracetic acid epoxy natural rubber latex.Japan's publication is equalled into the solution epoxidation systems of having reported ethylene-propylene rubber(EPR) among the 4-4204.The epoxidation process of butylbenzene thermoplastic elastomer in the vinyl acetic monomer solution system has been proposed among the international monopoly WO 98 14323.In above-mentioned various elastomeric ring oxidising processs all is to implement in solution or latex system.There is following shortcoming in these methods: for solution system, required quantity of solvent big (rubber: solvent wt/vol:1: 10～1: 40), postprocessing working procedures complexity, cost height, contaminate environment; Latex system then only is suitable for the epoxidation modification of natural rubber latex, also has aftertreatment problems such as flocculation such as latex, drying.
The objective of the invention is to overcome the defective of prior art, adopt reactive method for processing to implement elastomeric epoxidation.Reactive processing units commonly used is typical mixing tank, as batch mixer and forcing machine (continuous mixer).Reactive machining characteristics is exactly to realize that chemical reaction and forming process are integrated in processing units.
Method of the present invention is that elastomerics is added in the reactive processing units, adds a certain proportion of superoxide and dispersing additive down at 10～100 ℃, and reactive blending is after 3～20 minutes, but just discharging.
Reactive processing units of the present invention is Banburys mixing tank, single screw extrusion machine or twin screw extruder.
Elastomerics of the present invention is a butadiene type rubber, natural rubber, styrene-butadiene rubber(SBR), ethylene propylene ternary gel, thermoplastic elastomer.
Superoxide of the present invention is a benzoyl hydroperoxide, monoperphthalic acid, halo benzoyl hydroperoxide, a nitro benzoyl hydroperoxide.
Superoxide of the present invention and elastomeric ratio of components are preferably in 15～60% (wt%) at 10～90% (wt%).
Dispersing additive of the present invention is a talcum powder, kaolin, acidic white earth, potter's clay.
The present invention compared with prior art has following outstanding advantage: 1. propose first to adopt reactive working method to prepare the epoxidation elastomerics.It need not to increase manufacturing facilities, and production technique is simple, is a kind of economical and practical elastomer-modified method.2. do not use solvent in the reaction processing, can avoid or reduce the problem of environmental pollution that solvent brings.3. reaction conditions gentleness in the reaction processing, product postprocessing technology is simple, can significantly improve elastomeric cementability and with the compatibility of other polymkeric substance.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
The 24g cis-rich polybutadiene rubber is added in the pony mixer of laboratory, control rotating speed 32rpm, system temperature is 30 ℃, adds the mixture of being made up of 12g monoperphthalic acid and 12g talcum powder then, reactive blending 15 minutes.The content of epoxide group is 7.89% (volumetry analysis) in the epoxidized polybutadiene.
Embodiment 2:
The 20g cis-rich polybutadiene rubber is added in the pony mixer of laboratory, control rotating speed 20rpm, system temperature is 25 ℃, adds the mixture of being made up of 10g monoperphthalic acid and 20g talcum powder, reactive blending 15 minutes.The content of epoxide group is 8.54% in the epoxidized polybutadiene.
Embodiment 3:
The 40g cis-rich polybutadiene rubber is added in the pony mixer of laboratory, and control rotating speed 20rpm, system temperature are 20 ℃, add the 10g monoperphthalic acid then, reactive blending 15 minutes.The content of epoxide group is 5.08% in the epoxidized polybutadiene.
Embodiment 4:
40g styrene-butadiene rubber(SBR) is added in the pony mixer of laboratory, and 20 ℃ of control rotating speed 20rpm, system temperatures add the mixture of being made up of 7g monoperphthalic acid and 7g talcum powder, reactive blending 20 minutes then.The content of epoxide group is 4.89% in the epoxidation butadiene-styrene rubber.
Claims (8)
1, a kind of process for preparing epoxidized elastomer is characterized in that: in reactive processing units, superoxide and elastomerics react in the presence of certain temperature, time and certain dispersing additive.
2, method according to claim 1 is characterized in that described reactive processing units is typical mixing tank and forcing machine.
3, method according to claim 1 is characterized in that described elastomerics is butadiene type rubber, natural rubber, styrene-butadiene rubber(SBR), ethylene propylene ternary gel, thermoplastic elastomer.
4, method according to claim 1 is characterized in that described superoxide is benzoyl hydroperoxide, monoperphthalic acid, halo benzoyl hydroperoxide or a nitro benzoyl hydroperoxide.
5, method according to claim 1 is characterized in that described superoxide and elastomeric proportioning at 10～90% (wt%), are preferably in 15～60% (wt%).
6, method according to claim 1 is characterized in that described dispersing additive is talcum powder, acidic white earth, potter's clay.
7, method according to claim 1 is characterized in that the system temperature of reaction is 0～120 ℃.
8, method according to claim 1, the reaction times that it is characterized in that system is 3～30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114939 CN1121440C (en) | 2000-03-16 | 2000-03-16 | Process for preparing epoxidized elastomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00114939 CN1121440C (en) | 2000-03-16 | 2000-03-16 | Process for preparing epoxidized elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1263902A true CN1263902A (en) | 2000-08-23 |
| CN1121440C CN1121440C (en) | 2003-09-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00114939 Expired - Fee Related CN1121440C (en) | 2000-03-16 | 2000-03-16 | Process for preparing epoxidized elastomer |
Country Status (1)
| Country | Link |
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| CN (1) | CN1121440C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3181596A1 (en) * | 2015-12-17 | 2017-06-21 | Lanxess Inc. | Process for epoxidation of unsaturated polymer |
| US10822439B2 (en) | 2015-12-17 | 2020-11-03 | Arlanxeo Singapore Pte. Ltd. | Butyl rubber containing allylic alcohol |
| FR3101876A1 (en) | 2019-10-14 | 2021-04-16 | Compagnie Generale Des Etablissements Michelin | Process for preparing an epoxidized diene elastomer. |
| US11001648B2 (en) | 2015-12-17 | 2021-05-11 | Arlanxeo Singapore Pte. Ltd. | Treatment of epoxidized unsaturated isoolefin copolymers |
| CN114456489A (en) * | 2022-01-21 | 2022-05-10 | 台州市盛尔达塑业有限公司 | Gallon basin material and preparation method thereof |
-
2000
- 2000-03-16 CN CN 00114939 patent/CN1121440C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461840A (en) * | 2015-12-17 | 2021-10-01 | 阿朗新科新加坡私人有限公司 | Process for epoxidizing unsaturated polymers |
| US11001648B2 (en) | 2015-12-17 | 2021-05-11 | Arlanxeo Singapore Pte. Ltd. | Treatment of epoxidized unsaturated isoolefin copolymers |
| JP2019502797A (en) * | 2015-12-17 | 2019-01-31 | アランセオ・シンガポール・プライヴェート・リミテッド | Process for epoxidation of unsaturated polymers |
| EP3390463A4 (en) * | 2015-12-17 | 2019-06-05 | Arlanxeo Singapore Pte. Ltd. | Process for epoxidation of unsaturated polymer |
| US10774158B2 (en) | 2015-12-17 | 2020-09-15 | Arlanxeo Singapore Pte. Ltd. | Process for epoxidation of unsaturated polymer |
| US10822439B2 (en) | 2015-12-17 | 2020-11-03 | Arlanxeo Singapore Pte. Ltd. | Butyl rubber containing allylic alcohol |
| CN109196001A (en) * | 2015-12-17 | 2019-01-11 | 阿朗新科新加坡私人有限公司 | For making unsaturated polymer process for epoxidation |
| US11421052B2 (en) | 2015-12-17 | 2022-08-23 | Arlanxeo Singapore Pte. Ltd. | Treatment of epoxidized unsaturated isoolefin copolymers |
| CN109196001B (en) * | 2015-12-17 | 2021-10-01 | 阿朗新科新加坡私人有限公司 | Process for epoxidizing unsaturated polymers |
| EP3181596A1 (en) * | 2015-12-17 | 2017-06-21 | Lanxess Inc. | Process for epoxidation of unsaturated polymer |
| WO2021074507A1 (en) | 2019-10-14 | 2021-04-22 | Compagnie Generale Des Etablissements Michelin | Method for preparing an epoxidised diene elastomer |
| FR3101876A1 (en) | 2019-10-14 | 2021-04-16 | Compagnie Generale Des Etablissements Michelin | Process for preparing an epoxidized diene elastomer. |
| CN114456489A (en) * | 2022-01-21 | 2022-05-10 | 台州市盛尔达塑业有限公司 | Gallon basin material and preparation method thereof |
| CN114456489B (en) * | 2022-01-21 | 2024-01-23 | 台州市盛尔达塑业有限公司 | Gallon basin material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1121440C (en) | 2003-09-17 |
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