CN1666999A - Process for preparing in-situ graft modified rubber by using general rubber preparing device and its modifier - Google Patents
Process for preparing in-situ graft modified rubber by using general rubber preparing device and its modifier Download PDFInfo
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Abstract
This invention relates to a preparation method of home position grafting modification rubber and its modifier. The home position grafting accessory ingredient is small molecule organic matter with polyfunctional group of parents chemical activity. Chemical reaction is happened by it and carbon black and grafting reaction is happened by it and double bond equal functional group on rubber molecule chain, so interface binding power between organic macromolecule and dispersion level added in rubber. Stress can be greatly improved, compress permanent deformation be reduced of the rubber made by this invention. Aging quality, creep property and dynamic performance can be improved greatly, large structure carbon black dosage can be reduced greatly. Structure of cross linked network is improved to reduce fatigue heat buildup of materials and delay fatigue destructive process. Load carrying properties and useful life of elastomer structural material and product.
Description
(1) technical field
The present invention relates to a kind of chemical modification method and modified additive thereof of rubber, be meant especially and a kind ofly utilize general rubber preparing device to carry out rubber chemistry modification technology and modified additive thereof with the reaction of the compound of carbon containing-carbon unsaturated link(age), specifically be meant the preparation method that adopts general rubber preparing device situ-formed graft modified rubber and used modified additive thereof.
(2) background technology
Rubber is as a kind of macromolecular material, because performances such as its distinctive elasticity are used widely in all trades and professions.Carbon black and white carbon black are main as reinforcing filler in rubber industry, and the quality of rubber item is played an important role.But the interparticle autohemagglutination effect of carbon black and white carbon black is bigger, is difficult to disperse in rubber matrix, and owing to self be strong polarity inorganic particulate, and the interaction force between nonpolar organic matter such as natural rubber a little less than, influenced its effect.Simultaneously, must form firm combining between carbon black and the rubber molecular chain, cross-linked rubber could obtain more superior performance.
Because sooty inside is the condensed-nuclei aromatics structure, contain a large amount of carboxyls, lactone group, phenolic hydroxyl group and quinonyl etc. on its surface, therefore also there is a large amount of hydroxy functional groups on the surface of white carbon black, can utilize the method for surface chemical modification to improve the effect to rubber of carbon black and white carbon black.Carbon black in the past (white carbon black) surface chemical modification lattice mainly concentrate on industries such as printing ink, coating, main method has: SURFACTANT ADSORPTION facture, coupling agent treatment method, plasma processing method, surface graft modification method (comprising free radical mechanism, cationic mechanism, negatively charged ion mechanism etc.) etc. are greatly improved through the dispersiveness of carbon black in organic solvent and polymeric matrix of modification.But traditional chemical modification has two significant drawbacks, the one, and the chemical modification of carbon blacksurface particularly graft modification all is to finish before sneaking into polymkeric substance, adopts batch production methods such as reactor, and cost is higher, and environmental pollution is more serious; The 2nd, the carbon black after the grafting and the interface of superpolymer still mainly are physical actions, and effect is not really desirable.
(3) summary of the invention
The objective of the invention is to combine with interface between carbon black or the white carbon black, improve carbon black or the reinforcing effect of white carbon black in elastomeric material, and improve the dynamic property of rubber, propose a kind of preparation method of situ-formed graft modified rubber in order to improve rubber.
Another object of the present invention is to propose the used modified additive of preparation method that a kind of energy is fit to above-mentioned situ-formed graft modified rubber.
The objective of the invention is to be achieved through the following technical solutions.Adopt the preparation method of in-situ modified carbon black reinforced rubber, on the basis of former studies, by being combined, coupling agent treatment method and grafting chemic modified method be applied in compounding rubber and the sulfuration process, the small molecules coupling agent that promptly adopts two kinds of groups formations that contain amphiphilic chemical activity simultaneously is as modified additive, in rubber mixing process, make its while or priority and carbon black (white carbon black) surface in mixing and sulfidation, rubber macromolecule generation graft reaction, make and realize part chemical b ` power between carbon black (white carbon black) and rubber, because high two orders of magnitude of strength ratio physical action of chemical bond, therefore can strengthen the interface interaction power between carbon black and rubber greatly, increased the destruction of rubber simultaneously, dispersion level is also increased substantially carbon black (white carbon black) agglomerate.
The weight proportion of each raw material is in the inventive method: 100 parts of rubber, 5～100 parts of carbon black or white carbon blacks, 0.1～30 part of situ-formed graft auxiliary agent, conventional variety and consumption that other Synergist S-421 95s such as promotor, vulcanizing agent, activator, anti-aging agent, tenderizer etc. cooperate according to various rubber.Wherein rubber comprise the natural rubber, polyisoprene rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), paracril, ethylene-propylene rubber(EPR), chloroprene rubber, isoprene-isobutylene rubber, epichlorohydrin rubber, viton, silicon rubber, thiorubber, urethanes, regenerated rubber etc. of various kinds, specification and these rubber different ratioss and use rubber; Carbon black comprises N100 series, N200 series, N300 series, N400 series, N500 series, N600 series, N700 series, the carbon black of various kinds such as N800 series, N900 series, Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black and specification; White carbon black comprises the precipitated silica or the thermal silica of various specific surface areas, particle diameter; And the also usefulness of the white carbon black of the carbon black of various kinds and various kinds.
Used modified additive is in-situ modified grafting auxiliary agent in the inventive method, is a kind of small molecules coupling agent with amphiphilic chemical activity, and in-situ modified grafting auxiliary agent comprises and contains the active two kinds of groups of parents simultaneously.A kind of character of group is close inorganics, and easy and carbon black/white carbon black generation valence bond cooperation usefulness is mainly: acetoxyl group, halogen, alkoxyl group etc.; Another kind of group is close organism, and easy and elastomeric material generation chemical reaction is mainly: vinyl, methacryloxy, alkylamino, sulfydryl, chloropropyl, epoxy group(ing), alkyl sulfide alcohol radical, alkyl epoxy base or chain alkyl etc.; It also can be two or more above-mentioned micromolecular mixture; General rubber preparing device comprises the mill of various size, the Banbury mixer of various size.
The present invention includes following steps and processing condition:
The first step adds carbon black, white carbon black according to prescription in various rubber, situ-formed graft auxiliary agent, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 120～180 ℃ of high temperature mixing 2～30 minutes.
Second step was parked cooling with above-mentioned master batch, when the sizing material temperature in ℃ scope of normal temperature～100, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5～30 minutes according to prescription by common refining gluing method.
The 3rd step vulcanized the rubber unvulcanizate age overnight 1～60 minute in 100～200 ℃ according to common rubber vulcanization process.
The inventive method is to add situ-formed graft properties-correcting agent in containing sooty rubber, in compounding rubber and sulfidation, make and possess the active situ-formed graft auxiliary agent of parents chemical reaction takes place in the blended process on the spot, forming chemical bond with the functional group of carbon black inorganic filler surface such as (white carbon blacks) on the one hand combines, on the other hand with rubber molecular chain on functional groups such as two keys carry out graft reaction, thereby make and produce firm combining between carbon black and the rubber, form overall network, cause the raising of vulcanized rubber physical and mechanical properties.The elastomeric material of gained can significantly improve stress at definite elongation thus, reduce compression set, and make aging resistance, creep property and dynamic property etc. all obtain obvious improvement, can significantly reduce the consumption of super-normal structure black, improve the structure of cross-linked network, the heat build-up of material is significantly reduced, delay fatigue destructive process, the load-carrying properties and the work-ing life of improving elastomer structure material and goods.In addition, can also improve the ability that rubber is resisted hot oxygen, ozone, photoaging.Technology of the present invention is easy, does not need special modified device, directly adopts conventional rubber equipment such as high temperature mill or Banbury mixer to carry out modification, and modified effect is good, and non-environmental-pollution, has a good application prospect.
The situ-formed graft modified rubber material of the present invention's preparation can be used to prepare various cross-linked rubber goods, be applied to fields such as automotive industry, track traffic, industrial rubber articles, civilian rubber item, architectural waterproof material, electric wire, have broad application prospects.
The present invention has following advantage and beneficial effect compared with the prior art:
1, improves rubber and combine, significantly improve the physical and mechanical properties of cross-linked rubber with the interface of carbon black, white carbon black and other mineral fillers.
2, directly situ-formed graft properties-correcting agent is joined in the rubber that contains carbon black or white carbon black, in mixing and sulfidation, realize in-situ modified, with traditional carbon black modified technology relatively, do not need special modified device, technology is simple, it is convenient to implement, environmental pollution is little.
(4) embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1 Y-mercaptopropyl trimethoxysilane situ-formed graft modified carbon black filling natural rubber
According to the prescription of table 1 batching, 1# fills a prescription routinely that calendering process carries out.The 2# prescription adds the N330 carbon black according to prescription in natural rubber; The situ-formed graft modified additive is (containing two kinds of group synthetic of active sulfydryl of parents and alkoxyl group simultaneously) Y-mercaptopropyl trimethoxysilane, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 140 ℃ of high temperature mixing 8 minutes; After parking cool to room temperature, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5 minutes; Age overnight vulcanized 15 minutes in 150 ℃ according to common rubber vulcanization process.The physical and mechanical properties of gained cross-linked rubber is listed in table 2.As seen from the table, the situ-formed graft modification has good reinforcing effect to natural rubber, tensile strength, the stress at definite elongation of the cross-linked rubber behind the adding properties-correcting agent significantly improve, compression set obviously improves, simultaneously, DMTA analyzes demonstration, and 60 ℃ of following tg δ obviously reduce, and illustrates that the in-situ modified dynamic property of cross-linked rubber that makes improves.
Table 1 basic recipe
| ??1# | ??2# | |
| Natural rubber (3# smoked sheet) carbon black (N330) Y-mercaptopropyl trimethoxysilane zinc oxide stearic acid anti-aging agent RD antioxidant 4010NA Sulfur accelerant CZ altax Vulcanization accelerator TMTD | ??100 ??50 ??0 ??10.0 ??2.0 ??1.0 ??1.0 ??2.0 ??0.5 ??0.4 ??0.1 | ??100 ??50 ??5.0 ??10.0 ??2.0 ??1.0 ??1.0 ??2.0 ??0.5 ??0.4 ??0.1 |
The carbon black filled natural rubber vulcanized rubber performance of table 2
| Performance Detection: | ????1# | ??2# |
| Hardness, Shore A tensile strength, the Mpa tensile yield, % 300% stretches surely, MPa 200% stretches surely, MPa 100% stress at definite elongation, Mpa compression set, % (70 ℃ * 24h) DMTA analyzes tg δ (60 ℃) | ????72 ????25.4 ????473 ????15.0 ????8.7 ????3.5 ????28 ????0.121 | ??67 ??28.8 ??405 ??21.1 ??11.8 ??3.9 ??20 ??0.072 |
Embodiment 2 vinyltriethoxysilane situ-formed graft modified white carbon blacks are filled chloroprene rubber
According to the prescription of table 3,3# fills a prescription routinely that calendering process carries out.The 4# prescription adds white carbon black according to prescription in chloroprene rubber; The situ-formed graft modified additive is (containing two kinds of group synthetic of active vinyl of parents and alkoxyl group simultaneously) vinyltriethoxysilane, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 140 ℃ of high temperature mixing 8 minutes; After parking cool to room temperature, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5 minutes; Age overnight vulcanized 20 minutes in 160 ℃ according to common rubber vulcanization process.The physical and mechanical properties of gained cross-linked rubber is listed in table 4.As seen from the table, the carbon black filled chloroprene rubber of situ-formed graft modification dialogue has good reinforcing effect, and the tensile strength, the stress at definite elongation that add the cross-linked rubber behind the properties-correcting agent significantly improve, compression set, wear resisting property and dynamic property be improved significantly.
Table 3 basic recipe
| ????1# | ????2# | |
| Neoprene WRT white carbon Hi-Sil257N VTES magnesia stearic acid anti-aging agent RD antioxidant 4010NA zinc oxide accelerant N A-22 | ????100 ????30 ????0 ????3.0 ????2.0 ????1.0 ????1.0 ????5.0 ????0.8 | ????100 ????30 ????4.0 ????3.0 ????2.0 ????1.0 ????1.0 ????5.0 ????0.8 |
Table 4 white carbon black is filled the chloroprene rubber cured properties
| Performance Detection | ????1# | ??2# |
| Hardness, Shore A tensile strength, the Mpa tensile yield, % 300% stretches surely, MPa 200% stress at definite elongation, Mpa compression set, (70 ℃ * 24h) wear away volume, cm3/1.61km DMTA analyzes tg δ (60 ℃) to % | ????67 ????23.0 ????668 ????4.4 ????3.0 ????27 ????0.42 ????0.155 | ??63 ??24.6 ??470 ??14.0 ??7.8 ??11 ??0.34 ??0.122 |
Embodiment 3 N-β aminoethyls-γ aminopropyl trimethoxysilane situ-formed graft modified carbon black filled styrene butadiene rubber
According to the prescription of table 5,1# fills a prescription routinely that calendering process carries out.The 2# prescription adds the N330 carbon black according to prescription in styrene-butadiene rubber(SBR); The situ-formed graft modified additive is (containing the active two kinds of alkylaminos of parents and three kinds of group synthetic of alkoxyl group simultaneously) N-β aminoethyl-γ aminopropyl trimethoxysilane, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 140 ℃ of high temperature mixing 8 minutes; After parking cool to room temperature, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5 minutes; Age overnight vulcanized 15 minutes in 150 ℃ according to common rubber vulcanization process.The physical and mechanical properties of gained cross-linked rubber is listed in table 6.As seen from the table, the situ-formed graft modification has good reinforcing effect to carbon black filled styrene-butadiene rubber(SBR), tensile strength, the stress at definite elongation of the cross-linked rubber behind the adding properties-correcting agent significantly improve, compression set obviously improves, wears away volume and reduces, simultaneously, DMTA analyzes demonstration, and 60 ℃ of following tg δ obviously reduce, and illustrates that in-situ modified modification makes the dynamic property of cross-linked rubber improve.
Table 5 basic recipe
| ????1# | ????2# | |
| Butadiene-styrene rubber 1502 carbon blacks (N330) N-β aminoethyl-γ aminopropyl trimethoxysilane zinc oxide stearic acid anti-aging agent RD antioxidant 4010NA Sulfur accelerant CZ Vulcanization accelerator TMTD | ????100 ????50 ????0 ????5.0 ????2.0 ????1.0 ????1.0 ????1.8 ????1.2 ????0.1 | ????100 ????50 ????3.0 ????5.0 ????2.0 ????1.0 ????1.0 ????1.8 ????1.2 ????0.1 |
The carbon black filled styrene-butadiene rubber(SBR) cured properties of table 6
| Performance Detection | ????1# | ??2# |
| Hardness, Shore A tensile strength, the Mpa tensile yield, % 300% stretches surely, MPa 200% stretches surely, MPa 100% stress at definite elongation, Mpa compression set, (70 ℃ * 24h) wear away volume, cm3/1.61km DMTA analyzes tg δ (60 ℃) to % | ????64 ????21.3 ????499 ????8.6 ????4.4 ????2.0 ????3?1 ????0.12 ????0.185 | ??61 ??24.0 ??460 ??12.1 ??5.9 ??2.3 ??22 ??0.08 ??0.156 |
The embodiment 4 γ-carbon black filled chloroprene rubber of chloropropyl triethoxysilane situ-formed graft modified carbon black
According to the prescription of table 7,1# fills a prescription routinely that calendering process carries out.The 2# prescription adds thermally oxidized black according to prescription in chloroprene rubber; The situ-formed graft modified additive is (containing two kinds of group synthetic of active chloropropyl of parents and alkoxyl group simultaneously) γ-chloropropyl triethoxysilane, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 140 ℃ of high temperature mixing 8 minutes; After parking cool to room temperature, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5 minutes; Age overnight vulcanized 30 minutes in 150 ℃ according to common rubber vulcanization process.The physical and mechanical properties of gained cross-linked rubber is listed in table 8.As seen from the table, the situ-formed graft modification has good reinforcing effect to carbon black filled chloroprene rubber, tensile strength, the stress at definite elongation of the cross-linked rubber behind the adding properties-correcting agent significantly improve, compression set obviously improves, wears away volume and reduces, simultaneously, DMTA analyzes demonstration, and 60 ℃ of following tg δ obviously reduce, and illustrates that the in-situ modified dynamic property of cross-linked rubber that makes improves.
Table 7 basic recipe
| ????1# | ????2# | |
| Neoprene WRT channel black γ-chloropropyl triethoxysilane magnesia stearic acid anti-aging agent RD antioxidant 4010NA zinc oxide accelerant N A-22 | ????100 ????50 ????0 ? ????3.0 ????2.0 ????1.0 ????1.0 ????5.0 ????0.8 | ????100 ????50 ????6.0 ? ????3.0 ????2.0 ????1.0 ????1.0 ????5.0 ????0.8 |
The carbon black filled chloroprene rubber cured properties of table 8
| Performance Detection | ?1# | ??2# |
| Hardness, the ShoreA tensile strength, the Mpa tensile yield, % 200% stretches surely, MPa 100% stress at definite elongation, Mpa compression set, (70 ℃ * 24h) wear away volume, cm3/1.61km DMTA analyzes tg δ (60 ℃) to % | ?74 ?25.1 ?255 ?22.2 ?6.8 ?19 ?0.14 ?0.167 | ??71 ??26.7 ??208 ??25.4 ??2.3 ??11 ??0.09 ??0.149 |
By above-mentioned enforcement and Comparative Examples as can be known, present method has tangible reinforcing effect to various rubber such as carbon black or white carbon black filling natural rubber, chloroprene rubber, styrene-butadiene rubber(SBR), obviously improved tensile modulus, reduced compression set, improved dynamic property, and it is simple to have a situ-formed graft modified technique, can realize on general rubber preparing devices such as high temperature mill or Banbury mixer, be suitable for suitability for industrialized production, in rubber industry, can extensively adopt.
Claims (9)
1, the preparation method of general rubber preparing device situ-formed graft modified rubber, adopt the preparation method of in-situ modified carbon black reinforced rubber, by being combined, coupling agent treatment method and grafting chemic modified method be applied in compounding rubber and the sulfuration process, the small molecules coupling agent that promptly adopts two kinds of groups formations that contain amphiphilic chemical activity simultaneously is as modified additive, in rubber mixing process, make its while or priority and carbon black (white carbon black) surface in mixing and sulfidation, rubber macromolecule generation graft reaction, make and realize part chemical b ` power between carbon black (white carbon black) and rubber, the weight percent proportioning of described situ-formed graft modified carbon black or each raw material of white carbon black reinforced rubber is: 100 parts of rubber, 5～100 parts of carbon black or white carbon blacks, 0.1～30 part of situ-formed graft auxiliary agent, other Synergist S-421 95s such as promotor, vulcanizing agent, activator, anti-aging agent, conventional variety and consumption that tenderizer etc. cooperate according to various rubber, manufacture craft comprises the steps and processing condition:
The first step adds carbon black, white carbon black according to prescription in various rubber, situ-formed graft auxiliary agent, and other Synergist S-421 95s except that vulcanizing agent, promotor, under 120～180 ℃ of high temperature mixing 2～30 minutes.
Second step was parked cooling with above-mentioned master batch, when the sizing material temperature in ℃ scope of normal temperature～100, add Synergist S-421 95s such as promotor, vulcanizing agent, mixing at normal temperatures 5～30 minutes according to prescription by common refining gluing method.
The 3rd step vulcanized the rubber unvulcanizate age overnight 1～60 minute in 100～200 ℃ according to common rubber vulcanization process.
2, the preparation method of general rubber preparing device situ-formed graft modified rubber according to claim 1 is characterized in that: that described rubber comprises natural rubber, polyisoprene rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), paracril, ethylene-propylene rubber(EPR), chloroprene rubber, isoprene-isobutylene rubber, epichlorohydrin rubber, viton, silicon rubber, thiorubber, urethanes, regenerated rubber of various kinds, specification etc. and these rubber different ratioss and use rubber.
3, the preparation method of general rubber preparing device situ-formed graft modified rubber according to claim 1, it is characterized in that: carbon black comprises N100 series, N200 series, N300 series, N400 series, N500 series, N600 series, N700 series, the carbon black of various kinds such as N800 series, N900 series, Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black and specification.
4, the preparation method of general rubber preparing device situ-formed graft modified rubber according to claim 1 is characterized in that: white carbon black comprises the precipitated silica or the thermal silica of various specific surface areas, particle diameter.
5, the preparation method of general rubber preparing device situ-formed graft modified rubber according to claim 1, it is characterized in that: carbon black or white carbon black comprise that the sooty of various kinds is single or also use, the white carbon black of various kinds single or and usefulness, and the white carbon black of the carbon black of various kinds and various kinds and usefulness.
6, the preparation method's of general rubber preparing device situ-formed graft modified rubber according to claim 1 situ-formed graft properties-correcting agent, it is characterized in that: the small molecules coupling agent that the situ-formed graft modified additive constitutes for two kinds of groups that contain amphiphilic chemical activity simultaneously, coupling agent contains the active two kinds of groups of parents simultaneously, a kind of character of group is close inorganics easy and that carbon black/cooperation of white carbon black generation valence bond is used, and another kind of group is the close organism of easy and elastomeric material generation chemical reaction.
7, the preparation method's of general rubber preparing device situ-formed graft modified rubber according to claim 6 situ-formed graft properties-correcting agent is characterized in that: described close inorganics is any of acetoxyl group, halogen, alkoxyl group.
8, the preparation method's of general rubber preparing device situ-formed graft modified rubber according to claim 6 situ-formed graft modified additive is characterized in that: described close organism is any of vinyl, methacryloxy, alkylamino, sulfydryl, chloropropyl, epoxy group(ing), alkyl sulfide alcohol radical, alkyl epoxy base or chain alkyl.
9, according to the preparation method's of claim 6 or 7 or 8 described general rubber preparing device situ-formed graft modified rubbers situ-formed graft properties-correcting agent, it is characterized in that: described situ-formed graft modified additive also can be two or more above-mentioned micromolecular mixture.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102030931A (en) * | 2010-12-17 | 2011-04-27 | 徐州工业职业技术学院 | Chloroprene rubber pipe sizing material doped with co-chlorinated polyether reclaimed rubber |
| CN102942711A (en) * | 2012-11-12 | 2013-02-27 | 江苏东旭科技有限公司 | Processing technique for rubber |
| CN104629124A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Modified rubber compound and preparation method thereof, vulcanized rubber and application thereof |
| CN104017239B (en) * | 2014-04-28 | 2017-08-01 | 安徽世界村新材料有限公司 | A kind of preparation method of sulfhydryl modified activated carbon for regenerating waste or used rubber |
| CN110387073A (en) * | 2018-04-23 | 2019-10-29 | 中国石油天然气股份有限公司 | A kind of functional solution polymerized butadiene styrene rubber/white carbon black composite material and preparation method thereof |
| CN112980065A (en) * | 2021-03-03 | 2021-06-18 | 青岛科技大学 | Rubber composite material and preparation process and application thereof |
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| CN1324896A (en) * | 2001-07-05 | 2001-12-05 | 上海交通大学 | Rubber-plastic intermxed modified asphalt material with high high-temperature storage stability |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030931A (en) * | 2010-12-17 | 2011-04-27 | 徐州工业职业技术学院 | Chloroprene rubber pipe sizing material doped with co-chlorinated polyether reclaimed rubber |
| CN102942711A (en) * | 2012-11-12 | 2013-02-27 | 江苏东旭科技有限公司 | Processing technique for rubber |
| CN104629124A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Modified rubber compound and preparation method thereof, vulcanized rubber and application thereof |
| CN104629124B (en) * | 2013-11-12 | 2017-01-04 | 中国石油化工股份有限公司 | Modified rubber complex and preparation method thereof and vulcanite and application thereof |
| CN104017239B (en) * | 2014-04-28 | 2017-08-01 | 安徽世界村新材料有限公司 | A kind of preparation method of sulfhydryl modified activated carbon for regenerating waste or used rubber |
| CN110387073A (en) * | 2018-04-23 | 2019-10-29 | 中国石油天然气股份有限公司 | A kind of functional solution polymerized butadiene styrene rubber/white carbon black composite material and preparation method thereof |
| CN110387073B (en) * | 2018-04-23 | 2022-01-04 | 中国石油天然气股份有限公司 | Functionalized solution-polymerized styrene-butadiene rubber/white carbon black composite material and preparation method thereof |
| CN112980065A (en) * | 2021-03-03 | 2021-06-18 | 青岛科技大学 | Rubber composite material and preparation process and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1295255C (en) | 2007-01-17 |
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