CN103360628B - Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof - Google Patents
Loaded-type rubber vulcanization accelerant as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a loaded-type rubber vulcanization accelerant as well as a preparation method and an application thereof. The loaded-type rubber vulcanization accelerant is prepared by firstly, blending a silane coupling agent and an organic solvent into a 0.5-30% by mass solution, mixing with an inorganic carrier and forming into a mixture with a solid content of 2-80%, stirring for 6-30 hours at 40-100 DEG C, subsequently adding a rubber vulcanization accelerant with a mole number which is 1.0-1.8 times of that of the coupling agent into a product of the reaction, reacting for 10-20 hours under the protection of nitrogen at 50-80 DEG C, and finally filtering and drying the reaction product. The loaded-type rubber vulcanization accelerant is capable of remarkably improving the vulcanization acceleration efficiency of rubber and reducing environment pollution caused by an ordinary accelerant, has the functions of a reinforcing agent, an interfacial modifier and the like, is an efficient, multifunctional, environment-friendly and novel rubber chemical, and has a wide application prospect in the rubber industry.
Description
Technical field
The present invention relates to rubber ingredients and vulcanization of rubber field, specifically refer to a kind of Loaded-type rubber vulcanization accelerant and preparation method thereof and application.
Background technology
Vulcanization accelerator is most important kind in rubber ingredients, has the promotion vulcanization of rubber, shortens curing time, reduces curing temperature, reduces vulcanizing agent consumption and improves the plurality of advantages such as vulcanized rubber physical and mechanical properties.But the thiofide that at present industry is conventional exist help raise efficiency need further raising, function singleness, have the deficiencies such as pollution to environment.Along with modern industry and national defence to be produced rubber item and the improving constantly of service requirements, prepare efficient, multi-functional, environmental protection, the rubber vulcanization promotor of low cost becomes the trend of current rubber industry and auxiliary industry development.
Widely use loaded catalyst in chemical industry, by the active constituent load of catalyzer on some micron order or nano grade inorganic carrier, significantly can strengthen the activity of catalyst system, improve its catalytic efficiency to chemical reaction process.By the inspiration of loaded catalyst, we imagine, if thiofide is passed through certain mode load in some rubber inorganic filler surface, form Loaded-type rubber vulcanization accelerant, helping raise efficiency of vulcanization accelerator should be able to be improved, promotor can also be made to have the function such as strengthening agent, interface modifier concurrently, and promotor dust from flying and the pollution of migration to environment can be reduced.
According to above-mentioned imagination, the invention discloses a kind of method preparing Loaded-type rubber vulcanization accelerant.The loading type rubber accelerator prepared according to the method, the efficiency promoting the vulcanization of rubber can not only be significantly improved, the dispersion of filler in rubber matrix and interface cohesion can also be promoted, have the several functions such as promotor, strengthening agent, interface modifier concurrently, there is advantage in addition that reduce environmental pollution.This Loaded-type rubber vulcanization accelerant has no domestic and foreign literature report so far.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect such as helping raise efficiency of current thiofide existence has much room for improvement, function singleness, contaminate environment, a kind of preparation method of efficient, multi-functional, eco-friendly novel supported thiofide is provided.
Loaded-type rubber vulcanization accelerant of the present invention is that General Purpose Rubber vulcanization accelerator is formed the class rubber vulcanization promotor being covalently bound to inorganic filler surface and obtaining by silane coupling agent reaction.With the Loaded-type rubber vulcanization accelerant SiO that accelerator M and white carbon black are formed
2-g-M is example, its preparation principle schematically as follows:
The preparation method of a kind of Loaded-type rubber vulcanization accelerant disclosed by the invention, comprises the steps:
The first step, is made into the solution of mass concentration 0.5% ~ 30% by silane coupling agent and organic solvent, and is mixed to form with inorganic carrier the mixture that solid content is 2% ~ 80%, stirring reaction 6 ~ 30 hours under 40 DEG C ~ 100 DEG C conditions;
Second step, adds the rubber vulcanization accelerator that mole number is equivalent to coupling agent 1.0 ~ 1.3 times in the first step reaction product, under nitrogen protection, reacts 8 ~ 20 hours under 50 DEG C ~ 80 DEG C conditions.
3rd step, by above-mentioned reaction product filtration, drying, obtains described Loaded-type rubber vulcanization accelerant.
Further, in the preparation method of above-mentioned Loaded-type rubber vulcanization accelerant, described carrier comprises micron order or nano sized inorganic fillers, comprises white carbon black, kaolin, polynite, halloysite, attapulgite, talcum powder, mica powder, sepiolite powder, diatomite, silica flour, silica-alumina carbon black, boehmite; Described organic solvent comprises ethanol, Virahol, toluene, acetone, butanone, ether, vinyl acetic monomer; Described coupling agent comprises γ-chloropropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, γ-aminopropyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl dimethylethoxysilane, γ-glycidoxypropyltrime,hoxysilane; Described vulcanization accelerator comprises 2-mercaptobenzothiazole (captax), N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ), N tert butyl benzothiazole 2 sulfenamide (accelerator NS), vulkacit D (vulkacit D) and derivative thereof.
The present invention's synthesis be that the Loaded-type rubber vulcanization accelerant of carrier can be applicable in natural rubber and various synthetic rubber with mineral filler, they have significant vulcanization accelerator effect, significantly can shorten the sulfurizing time of rubber unvulcanizate, reduce sulfuration activation energy, improve the apparent crosslinking of cross-linked rubber, the mechanical property of cross-linked rubber can also be significantly improved, show obvious strengthening action.
Compared with existing vulcanization accelerator, tool of the present invention has the following advantages:
(1) inorganic carrier in Loaded-type rubber vulcanization accelerant can produce activation to promotor, there is larger specific surface area simultaneously, larger reacting environment can be provided for vulcanization reaction, in addition because the existence of coupling agent makes promotor be easy to the dispersion in rubber, thus Loaded-type rubber vulcanization accelerant can accelerate vulcanization reaction speed, improves the efficiency that promotor promotes sulfuration.
(2) in Loaded-type rubber vulcanization accelerant silane coupling agent and organic promoter by being covalently bonded on inorganic filler surface, surface modification effect can be produced to mineral filler, the consistency of reinforcing filler and rubber matrix, improve the dispersion of filler in rubber matrix and interface cohesion, thus improve filler to the reinforcing effect of rubber.
(3) Loaded-type rubber vulcanization accelerant can reduce promotor in the dust from flying refined in the course of processing such as glue and sulfuration and volatilization; be conducive to the environment protection in workshop; the fire and explosive hazard of small molecules promotor dust can also be reduced, migration and the volatilization of promotor residue in cross-linked rubber can be greatly reduced in addition.
(4) preparation flow of Loaded-type rubber vulcanization accelerant provided by the invention is easy, and technique is simple, and solvent toxicity is little and can reuse, and is conducive to reducing costs and industrialization promotion.
Accompanying drawing explanation
Fig. 1 is supported sulfided promotor (SiO in embodiment 1
2-g-M) and coupling agent modified rear silicon-dioxide (m-SiO
2) infrared spectrogram.
Fig. 2 is silicon-dioxide (SiO in embodiment 1
2), coupling agent modified silicon-dioxide (m-SiO
2) and Loaded-type rubber vulcanization accelerant (SiO
2-g-M) thermogravimetric curve.
Embodiment
In order to describe better and understand the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
By 20g precipitated silica (SiO
2) be distributed in 300ml ethanol, add 4g γ-chloropropyl triethoxysilane, react 10 hours under 70 DEG C of conditions, obtain coupling agent modified silicon-dioxide (m-SiO
2).Then add 2.8g vulcanization accelerator 2-benzothiazolyl mercaptan (M), react 18 hours under 80 DEG C of conditions, product centrifugation also by washing with alcohol, is put into vacuum drying oven and is dried to constant weight, obtain supported sulfided promotor SiO
2-g-M.
The infrared spectra of above-mentioned supported sulfided promotor after solvent extraction (accompanying drawing 1) shows, at 1457cm
-1and 1515cm
-1place adds absorption band, and corresponding to the absorption of vibrations of phenyl ring in captax, the function served as bridge of captax by coupling agent is described, is successfully grafted on the surface of silicon-dioxide, synthesized product is target product.Thermogravimetric analysis (accompanying drawing 2) shows, SiO
2in-g-M, the massfraction of captax is 2.23%.
With supported sulfided promotor SiO
2the basic recipe of styrene-butadiene rubber(SBR) prepared by-g-M or styrene-butadiene rubber(SBR)/white carbon black composite material is in table 1, and the vulcanization characteristics parameter of corresponding rubber unvulcanizate is in table 2.As seen from Table 2, compared with promoting M with the non-load sulfuration of equal parts, SiO
2-g-M can significantly improve vulcanization rate, shortens sulfurizing time Tc90 and time of scorch Ts2, reduces vulcanization reaction active energy, improves cross-linked rubber cross-linking density.
Loaded-type rubber vulcanization accelerant SiO used by table 3
2the mechanical property of styrene-butadiene rubber(SBR)/white carbon black composite material prepared by-g-M.Can find out, supported sulfided promotor SiO
2-g-M is compared with the non-load accelerator M of equal parts, and to the tensile strength improving cross-linked rubber, the mechanical property such as stress at definite elongation and tear strength has better effect.
Table 1
In table 1, unit is mass parts (phr); Loading type promotor SiO in No. 3 formulas
2-g-M consumption is 24.6phr, and thermal weight loss result shows every 24.6phrSiO
2containing captax phr in-g-M.1, the filler SiO of No. 2 formulas
2consumption is 23.6phr, with SiO in formula 3
2carrier S iO contained by-g-M
2measure identical; In table, antioxidant 4010NA is N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
Table 2
Embodiment 2
Be dissolved in 80g acetone by 15g γ-r-chloropropyl trimethoxyl silane, and mix with 150g halloysite nanotubes (HNTs), stirring reaction 20 hours under 50 DEG C of conditions, obtains coupling agent modified halloysite nanotubes (m-HNTs) dispersion liquid.Then 12g accelerator M (2-benzothiazolyl mercaptan) is added, stirring reaction 20 hours at 50 DEG C.Product is filtered, is dried to constant weight, obtains supported sulfided vulkacit H NTs-g-M.
Product synthesized by infrared spectra display is target product.In thermogravimetric analysis display HNTs-g-M, the massfraction of captax is 3.78%.The basic recipe of the styrene-butadiene rubber(SBR)/halloysite composite material prepared with HNTs-g-M is in table 4, and the curing parameter of corresponding rubber unvulcanizate is in table 5.As seen from Table 5, compared with promoting M with the non-load sulfuration of equal parts, HNTs-g-M can significantly improve vulcanization rate, shortens rubber unvulcanizate sulfurizing time Tc90, and reduces vulcanization reaction active energy.
Table 6 is the mechanical properties of the styrene-butadiene rubber(SBR)/halloysite composite material prepared with Loaded-type rubber vulcanization accelerant HNTs-g-M.Can find out, Loaded-type rubber vulcanization accelerant HNTs-g-M is compared with the non-load accelerator M of equal parts, and to the tensile strength improving cross-linked rubber, the mechanical property such as stress at definite elongation and tear strength has better effect.
In table 4, unit is mass parts (phr); In No. 6 formulas, loading type vulkacit H NTs-g-M consumption is 27.3 parts, and it is 2phr that thermal weight loss result shows contained captax in every 27.3phr.4, the filler HNTs consumption of No. 5 formulas is 25.3phr, non-load captax consumption 2phr.
Table 5
Table 6
Embodiment 3
12g gamma-mercaptopropyltriethoxysilane is dissolved in 300ml toluene; add 45g fumed silica dispersed with stirring again and become mixed solution; react 8 hours under 90 DEG C of conditions; then 12g vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide (accelerant CZ) is added, 80 DEG C of stirring reactions 8 hours under nitrogen protection.Product is filtered, dry, obtain final product loading type promotor SiO
2-g-CZ.
Infrared spectra and nucleus magnetic resonance display, synthesized product is target product SiO
2-g-CZ.Thermogravimetric analysis shows, and in Loaded-type rubber vulcanization accelerant, the massfraction of N-cyclohexyl-2-[4-morpholinodithio sulphenamide is 3.14%.Table 7 shows, compared with the non-load accelerator CZ of equal parts, HNTs-g-CZ can significantly improve vulcanization rate, shortens rubber unvulcanizate sulfurizing time Tc90, and can keep longer time of scorch Ts2, can also significantly improve the mechanical property of cross-linked rubber.
Table 7
In table 7, unit is mass parts (phr); SiO in No. 8 samples
2-g-CZ consumption is 24.6phr, shows the SiO of every 24.6phr according to thermal weight loss result
2containing accelerant CZ 1.5phr in-g-CZ.SiO additional in No. 7 samples
2amount and SiO
2contained SiO in-g-CZ
2identical, be 23.1phr;
Embodiment 4
By 15g Dispersion of Kaolin in 300ml ethanol, add 4g γ-aminopropyl triethoxysilane in above-mentioned mixed solution, stirring reaction 10 hours at 70 DEG C.Then 4g vulcanization accelerator N tert butyl benzothiazole 2 sulfenamide (accelerator NS) is added; the lower 60 DEG C of reactions of nitrogen protection 24 hours; product filters and uses washing with alcohol, puts into vacuum drying oven and is dried to constant weight and obtains loading type rubber accelerator Kaolin-g-NS.
Thermogravimetic analysis (TGA) shows, and in Loaded-type rubber vulcanization accelerant, the massfraction of the N-tertiary butyl-2-benzothiazole sulfonamide is 2.54%.Compared with the non-load vulcanization accelerator NS of equal parts, Kaolin-g-CZ can significantly improve vulcanization rate, shortens rubber unvulcanizate sulfurizing time Tc90, and can keep longer time of scorch Ts2, can also significantly improve the mechanical property of cross-linked rubber.
Embodiment 5
4g vinyltriethoxysilane is dissolved in 300ml ethanol, adds 20g attapulgite and form dispersion liquid, stirring reaction 10 hours at 70 DEG C.Then add 4g accelerator D (vulkacit D), the lower 60 DEG C of reactions of nitrogen protection 12 hours, product filters and uses washing with alcohol, puts into vacuum drying oven and is dried to constant weight, obtains loading type rubber accelerator attapulgite-g-D.
Claims (4)
1.
a preparation method for Loaded-type rubber vulcanization accelerant, is characterized in that, comprises the steps:
the first step, is made into the solution of mass concentration 0.5% ~ 30% by silane coupling agent and organic solvent, and is mixed to form with inorganic carrier the mixture that solid content is 2% ~ 80%, stirring reaction 6 ~ 30 hours under 40 DEG C ~ 100 DEG C conditions; Described silane coupling agent comprises the one in γ-chloropropyl triethoxysilane, γ-r-chloropropyl trimethoxyl silane, γ-aminopropyl triethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl dimethylethoxysilane, γ-glycidoxypropyltrime,hoxysilane; Described inorganic carrier comprises the one in white carbon black, halloysite, talcum powder, mica powder, diatomite, silica flour, silica-alumina carbon black, boehmite;
second step, adds the thiofide that mole number is equivalent to silane coupling agent 1.0 ~ 1.3 times in the first step reaction product, under nitrogen protection, reacts 8 ~ 20 hours under 50 DEG C ~ 80 DEG C conditions; Described vulcanization accelerator comprises the one in 2-mercaptobenzothiazole (captax), N cyclohexyl 2 benzothiazole sulfenamide (accelerant CZ), N tert butyl benzothiazole 2 sulfenamide (accelerator NS), vulkacit D (vulkacit D) and derivative thereof;
3rd step, by above-mentioned reaction product filtration, drying, obtains described Loaded-type rubber vulcanization accelerant.
2.
the preparation method of a kind of Loaded-type rubber vulcanization accelerant according to claim 1, is characterized in that, described organic solvent comprises one or more the mixed solvent in ethanol, Virahol, toluene, acetone, butanone, ether, vinyl acetic monomer.
3.
the Loaded-type rubber vulcanization accelerant obtained by preparation method described in any one of claim 1 ~ 2.
4.
the application of Loaded-type rubber vulcanization accelerant described in claim 3, is characterized in that being applied in natural rubber or various synthetic rubber.
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| CN104356424B (en) * | 2014-11-26 | 2018-02-06 | 山东阳谷华泰化工股份有限公司 | A kind of preparation method of low zinc vulcanizing activator |
| CN106700160A (en) * | 2016-11-21 | 2017-05-24 | 华南理工大学 | Preparation method of supported rubber vulcanizing agent and application thereof |
| CN106750666B (en) * | 2016-11-22 | 2018-10-30 | 青岛科技大学 | A kind of preparation method and applications of plant polyphenol base rubber accelerator |
| CN106496700A (en) * | 2016-11-30 | 2017-03-15 | 华南理工大学 | A kind of Loaded-type rubber vulcanization accelerant and preparation method and application |
| CN108129697A (en) * | 2017-12-29 | 2018-06-08 | 海南大学 | A kind of white carbon load xanthates and preparation method and application |
| CN111303489A (en) * | 2020-03-30 | 2020-06-19 | 华南理工大学 | Environment-friendly rubber accelerator modified filler and preparation method and application thereof |
| CN114437408B (en) * | 2020-10-16 | 2023-07-21 | 中国石油化工股份有限公司 | Modified peroxide vulcanizing agent and preparation method and application thereof |
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