CN104861319A - Vulcanization accelerator composition as well as preparation method and application thereof - Google Patents
Vulcanization accelerator composition as well as preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses vulcanization accelerator composition. The vulcanization accelerator composition comprises pre-dispersion host master batch granules and pre-dispersion ligand master batch granules, wherein the pre-dispersion host master batch granules comprise 3-mythyl-2-thiazolidinone, the pre-dispersion ligand master batch granules comprise mixtures of organic amine compounds and benzimidazole compounds; each type of master batch granules further comprise rubber, stearic acid, pentaerythritol aliphatic ester, ethylene-vinyl acetate copolymer and/or ethylene-vinyl ester copolymer, rubber in liquid polar plasticizers and at least one other ingredient. Through cooperation of the two types of master batch granules, vulcanization of a chloroprene rubber system is synergistically accelerated, the vulcanization characteristic of the master batch granules is equivalent to that of ETU (ethylene thiourea), the processing property doesn't change, the comprehensive physical and mechanical properties are equivalent, the compression set performance of a product of the master batch granules is superior to that of ETU vulcanization accelerator products, and the product quality is improved.
Description
Technical field
The present invention relates to a kind of rubber ingredients, be specifically related to a kind of vulcanization accelerator composition and method of making the same of being formed by pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles and application.
Background technology
Thiazoles and sulfenamide thiofide are a kind of materials that can promote sulfur vulcanization effect, sulfur sulfurizing agent can be impelled to activate, thus the crosslinking reaction accelerated between sulfur sulfurizing agent and rubber molecule, reach the practical functions such as the physical and mechanical properties shortening curing time, reduction curing temperature, minimizing vulcanizing agent consumption and improve rubber.Can be used alone, also can with dithiocarbamate(s), thiurams, Thiourea, guanidine class and other basic-type accelerator and use, mainly for the manufacture of tire, adhesive tape, rubber overshoes and other industrial rubber articles.
Apply more thiofide in the market and have MBT, MBTS, CBS, TBBS, ZDEC, ZDMC, ZDBC, TMTD, TMTM, ETU, DETU, DPG, DOTG etc., according to the difference of rubbery system needing sulfuration, thus the thiofide that choice for use is different, such as, chloroprene rubber has excellent thermotolerance, weathering resistance, wear resistance, oil-proofness, flame retardant resistance, is widely used in manufacturing sebific duct, adhesive tape, electric wire foreskin, cable sheath, printing rubber roll, offset plate, liner and damping washer or pad, vinylthiourea (ETU, toxicity is designated T, R61, R22), because it can provide cross-linked rubber stress at definite elongation to chloroprene rubber, rebound resilience, compression set and resistant to heat aging optimum balance, become the vulcanization accelerator that chloroprene rubber vulcanization system relies on use always, but vinylthiourea ETU a kind ofly has direct toxicity and indirect toxicity and has the compound of potential carinogenicity, its use in technological process is not only serious pollutes environment, more endanger the healthy of people, therefore, from environmental angle, be not a kind of vulcanization accelerator product of recommendation.But due to the specificity that existing vulcanization accelerator promotes the vulcanization of rubber, it can not replace with other rubber accelerator existing, such as, the active function groups of thiazoles MBT or MBTS, sulfenamide CBS or TBBS, thiurams TMTD or TMTM promotor is applicable to the dience rubber producing tire, the sulfuration promoting chloroprene rubber cannot be used at all, and the processing safety improving chloroprene rubber sulfuration can only be used for.
Summary of the invention
Have the problem of toxicity and carinogenicity for solving ETU vulcanization accelerator in prior art, and then provide a kind of new environment-friendly type vulcanization accelerator, the rubber item performance formed by its sulfuration is suitable with the rubber item performance of use ETU vulcanization accelerator.
For this reason, the technical scheme that the application takes is,
A kind of vulcanization accelerator composition, comprising pre-dispersed main body masterbatch particles, is 100 mass parts to prepare the raw material of described pre-dispersed main body masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material, 3-methyl-2-thiazole thione 10 ~ 90 mass parts, rubber 5 ~ 90 mass parts.
Above-mentioned vulcanization accelerator composition, the raw material of described pre-dispersed main body masterbatch particles also comprises, stearic acid 1 ~ 10 mass parts, pentaerythritol fatty ester 1 ~ 10 mass parts, ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts, liquid polarity softening agent 1 ~ 10 mass parts.
Above-mentioned vulcanization accelerator composition, also comprises pre-dispersed part masterbatch particles, is 100 mass parts to prepare the raw material of described pre-dispersed part masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material,
Ligand compound 10-90 mass parts, rubber 5 ~ 90 mass parts, described ligand compound is mass ratio is the organic amine compound of 1:9-9:1 and the mixture of benzimidazole compound formation.
Above-mentioned vulcanization accelerator composition, described organic amine compound is diazabicylo or 1,8-diazacyclo laurylene.
Above-mentioned vulcanization accelerator composition, described benzimidazole compound is 2-mercaptobenzimidazole MBI, 2-mercaptobenzimidazole zinc ZMBI, 2-thiol group tolimidazole MMBI or 2-thiol group tolimidazole zinc ZMMBI.
Above-mentioned vulcanization accelerator composition, the raw material of described pre-dispersed part masterbatch particles also comprises,
Stearic acid 1 ~ 10 mass parts,
Pentaerythritol fatty ester 1 ~ 10 mass parts,
Ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts,
Liquid polarity softening agent 1 ~ 10 mass parts.
Above-mentioned vulcanization accelerator composition is 100 parts to prepare the raw material of described pre-dispersed part masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material,
Organic amine compound 10-60 mass parts,
Benzimidazole compound 10-50 mass parts,
Rubber 5 ~ 90 mass parts,
Stearic acid 1 ~ 10 mass parts,
Ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts,
Pentaerythritol fatty ester 1 ~ 10 mass parts,
Liquid polarity softening agent 1 ~ 10 mass parts.
Above-mentioned vulcanization accelerator composition, described rubber is polyacrylic rubber ACM, ethylene-acrylate copolymers rubber AEM, urethanes PUR, isoprene-isobutylene rubber IIR, chlorinated butyl rubber CIIR, brominated butyl rubber BIIR, cis-1,4-polybutadiene rubber BR, homopolymerization chlorohydrin rubber CO, copolymerization chlorohydrin rubber ECO, chloroprene rubber CR, chlorinated polyethylene rubber CPE, chlorosulfonated polyethylene rubber CSM, ethylene propylene rubber EPM, terpolymer EP rubber EPDM, viton FPM, trifluoropropyl siloxane FVMQ, polyisoprene rubber IR, Natural rubber, styrene butadiene rubber sbr, one or more in paracril NBR.
Above-mentioned vulcanization accelerator composition, described rubber is chlorinated polyethylene rubber, and its cl content is 30 ~ 45wt%, mooney viscosity ML125 DEG C of (1+4)=45 ~ 85.
Above-mentioned vulcanization accelerator composition, described pentaerythritol fatty ester is tetramethylolmethane tristearate and/or pentaerythritol tetrastearate.
Above-mentioned vulcanization accelerator composition, described liquid polarity softening agent be in dibutyl phthalate DBP, dioctyl phthalate (DOP) DOP, diisononyl phthalate DINP, Octyl adipate DOA, dioctyl azelate DOZ, dioctyl sebacate DOS, Tritolyl Phosphate TCP, liquid chlorinated paraffin and epoxidized fatty acid in one or more.
Above-mentioned vulcanization accelerator composition, the mass ratio of described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles is 1:100-100:1.
The preparation method of above-mentioned vulcanization accelerator composition, comprises,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35-100 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35-100 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles are mixed, obtain described vulcanization accelerator composition.
The preparation method of above-mentioned vulcanization accelerator composition, the melting temperature of described step (1) and step (2) is 35-55 DEG C.
Above-mentioned vulcanization accelerator composition is promoting the application in the vulcanization of rubber.
Above-mentioned vulcanization accelerator composition is promoting the application in the vulcanization of rubber; respectively described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles are joined in finished composition system, or join after described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles mixing in finished composition system.
Compared with prior art, tool of the present invention has the following advantages,
(1) vulcanization accelerator in the application comprises a kind of pre-dispersed main body masterbatch particles, it comprises 3-methyl-2-thiazole thione and 5 ~ 90 parts of rubber of 10 ~ 90 parts, the pre-dispersed main body masterbatch particles of the application can be used for the sulfuration promoting chloroprene rubber, and there is no direct toxicity and indirect toxicity, solve the environmental issue in chloroprene rubber process of producing product.
(2) the application uses the promotor formed with pre-dispersed main body masterbatch particles and the composite form of pre-dispersed part masterbatch particles first, replace existing ETU vulcanization accelerator, wherein pre-dispersed main body masterbatch particles adopts the masterbatch particles that 3-methyl-2-thiazole thione is formed, the masterbatch particles that pre-dispersed part masterbatch particles adopts the mixture of organic amine compound and benzimidazole compound to be formed, two kinds of masterbatch particles are with the use of the sulfuration of collaborative promotion chloroprene rubber system, the vulcanization characteristics of its vulcanization characteristics and ETU is suitable, process industrial art performance does not change, comprehensive physical mechanical property is suitable, and the compression set performance of its goods is higher than the compression set performance of ETU vulcanization accelerator system goods, improve the quality of product.
(3) a certain amount of stearic acid is also comprised respectively in the pre-dispersed main body masterbatch particles in the application and pre-dispersed part masterbatch particles, pentaerythritol fatty ester, ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts and liquid polarity softening agent, above-mentioned raw materials and rubber compounding use the thermal softening carrier being formed and have excellent compatibility, 3-methyl-2-the thiazole thione in two kinds of masterbatch particles can be made, organic amine compound and benzimidazole compound are dispersed at lower than 55 DEG C carries out mixing granulating in the carrier, thus make it disperse and distributed uniform in rubber item system, improve final product quality.And save energy consumption, under avoiding room temperature, adhesion is lumpd, and is convenient to transport, weigh batching accurately facilitates.
(4) organic amine compound and the benzimidazole compound of the liquid state in the pre-dispersed part masterbatch particles of the application use, in both mixing processes, the organic amine compound of liquid state is absorbed by powdery benzimidazole compound and becomes " dry powder body ", avoids the loss that organic amine compound causes the adhesion of processing units.
(5) vulcanization accelerator of the application can be applicable to promote the halogen-containing rubber of sulfuration (chlorination or brominated butyl rubber CIIR or BIIR), homopolymerization or copolymerization chlorohydrin rubber CO or ECO, chloroprene rubber CR, chlorinated polyethylene rubber CPE (CM), chlorosulfonated polyethylene rubber CSM, viton FPM, trifluoropropyl siloxane FVMQ, paracril NBR/PVC etc.Especially sulfuration chloroprene rubber CR, for the manufacture of automotive hose, automobile sealed goods, automobile travelling belt and Timing Belt, automobile sheath, industrial sebific duct, building sealing member, agricultural machine travelling belt, Duprene rubber foamed goods etc. neoprene neoprene.
At present, the all marketable material of Chemical market are all applicable to the vulcanization accelerator preparing the application, as long as 3-methyl-2-thiazole thione can be prepared into pre-dispersed main body masterbatch particles, and obtain the pre-dispersed part masterbatch particles of organic amine compound and benzimidazole compound.The rubber preparing corresponding masterbatch particles is the rubber that can be used for producing masterbatch particles all in prior art, such as polyacrylic rubber ACM, ethylene-acrylate copolymers rubber AEM, urethanes PUR, isoprene-isobutylene rubber IIR, chlorinated butyl rubber CIIR, brominated butyl rubber BIIR, cis-1,4-polybutadiene rubber BR, homopolymerization chlorohydrin rubber CO, copolymerization chlorohydrin rubber ECO, chloroprene rubber CR, chlorosulfonated polyethylene rubber CSM, ethylene propylene rubber EPM, terpolymer EP rubber EPDM, viton FPM, trifluoropropyl siloxane FVMQ, polyisoprene rubber IR, Natural rubber, styrene butadiene rubber sbr, one or more in paracril NBR.
Embodiment
For ease of comparing, in the embodiment of the present application, choice for use is chlorinated polyethylene rubber, and its cl content is 30 ~ 45wt%, mooney viscosity ML125 DEG C of (1+4)=45 ~ 85.Vinyl acetate between to for plastic mass content 45 ± 1.5% in ethylene-vinyl acetate copolymer, the mass content 45 ± 1.5% of vinyl acetate in ethylene-vinyl acetate copolymer, both melt flow rate (MFR)s under 190 DEG C/21.2N, 5-15g/10min, pentaerythritol fatty ester fusing point is 57 DEG C, acid number: 2mgKOH/g, hydroxyl value: 60mgKOH/g.
Embodiment 1
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 10g, chlorinated polyethylene rubber 80g, stearic acid 2g, pentaerythritol fatty ester 2g, ethylene-vinyl acetate copolymer EVA2g, ethylene-vinyl acetate copolymer EVM2g dioctyl sebacate DOS 1g and dibutyl phthalate DBP1g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 1g, 2-mercaptobenzimidazole zinc ZMBI 9g, chlorinated polyethylene rubber 80g, stearic acid 2g, pentaerythritol fatty ester 2g, ethylene-vinyl acetate copolymer EVA2g, ethylene-vinyl acetate copolymer EVM2g, dioctyl sebacate DOS 1g and dibutyl phthalate DBP.
Pentaerythritol fatty ester described in the present embodiment is pentaerythritol tetrastearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S1.
Embodiment 2
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 90g, chlorinated polyethylene rubber 5g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM1g Octyl adipate DOA0.5g and dioctyl phthalate (DOP) DOP 0.5g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 60g, 2-thiol group tolimidazole MMBI 20g, chlorinated polyethylene rubber 10g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA2g, ethylene-vinyl acetate copolymer EVM4g, dioctyl phthalate (DOP) DOP 1g and dioctyl sebacate DOS 1g.
Pentaerythritol fatty ester described in the present embodiment is pentaerythritol tetrastearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 55 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 40 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 20:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S2.
Embodiment 3
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, and the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 10g, chlorinated polyethylene rubber 90g.
The raw material preparing pre-dispersed part masterbatch particles comprises, 1,8-diazacyclo laurylene 5g, 2-thiol group tolimidazole zinc ZMMBI5g, chlorinated polyethylene rubber 90g.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 90 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 80 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 50:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S3.
Embodiment 4
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 60g, chlorinated polyethylene rubber 17g, stearic acid 10g, pentaerythritol fatty ester 8g, ethylene-vinyl acetate copolymer EVA1g Tritolyl Phosphate TCP1g, liquid chlorinated paraffin 1g and epoxidized fatty acid 2g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 15g, 2-mercaptobenzimidazole MBI 50g, chlorinated polyethylene rubber 6g, stearic acid 8g, pentaerythritol fatty ester 5g, ethylene-vinyl acetate copolymer EVA4g, ethylene-vinyl acetate copolymer EVM2g liquid chlorinated paraffin 2g, epoxidized fatty acid 2g and dioctyl sebacate DOS 6g.
Pentaerythritol fatty ester described in the present embodiment is pentaerythritol tetrastearate and tetramethylolmethane tristearate take mass ratio as the mixture that 2:3 is formed.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 45 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 50 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 80:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S4.
Embodiment 5
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 40g, chlorinated polyethylene rubber 40g, stearic acid 3g, tetramethylolmethane fat sour 10g, ethylene-vinyl acetate copolymer EVM1g, dioctyl sebacate DOS 3g and epoxidized fatty acid 3g.
The raw material preparing pre-dispersed part masterbatch particles comprises, 1,8-diazacyclo laurylene 50g, 2-mercaptobenzimidazole zinc ZMBI 40g, chlorinated polyethylene rubber 5g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM1g, dioctyl sebacate DOS 3g and epoxidized fatty acid 2g.
Pentaerythritol fatty ester described in the present embodiment is tetramethylolmethane tristearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 100:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S5.
Embodiment 6
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 50g, chlorinated polyethylene rubber 23g, stearic acid 5g, pentaerythritol fatty ester 3g, ethylene-vinyl acetate copolymer EVA2g, ethylene-vinyl acetate copolymer EVM8g and, dioctyl sebacate DOS 3g and epoxidized fatty acid 6g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 20g, 2-thiol group tolimidazole MMBI 30g, chlorinated polyethylene rubber 23g, stearic acid 5g, pentaerythritol fatty ester 3g, ethylene-vinyl acetate copolymer EVA8g, ethylene-vinyl acetate copolymer EVM2g, liquid chlorinated paraffin 3g and epoxidized fatty acid 6g.
Pentaerythritol fatty ester described in the present embodiment is pentaerythritol tetrastearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 50 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 50 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:60 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S6.
Embodiment 7
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 65g, chlorinated polyethylene rubber 6g, stearic acid 8g, pentaerythritol fatty ester 5g, ethylene-vinyl acetate copolymer EVA2g, ethylene-vinyl acetate copolymer EVM4g, Tritolyl Phosphate TCP3g and dibutyl phthalate DBP 7g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 40g, 2-thiol group tolimidazole zinc ZMMBI 20g, chlorinated polyethylene rubber 17g, stearic acid 10g, pentaerythritol fatty ester 8g, ethylene-vinyl acetate copolymer EVA1g, Tritolyl Phosphate TCP3g and dibutyl phthalate DBP 1g.
Pentaerythritol fatty ester described in the present embodiment is tetramethylolmethane tristearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 50 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 45 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:70 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S7.
Embodiment 8
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 80g, chlorinated polyethylene rubber 10g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA4g, ethylene-vinyl acetate copolymer EVM2g, Tritolyl Phosphate TCP1g and epoxidized fatty acid 1g.
The raw material preparing pre-dispersed part masterbatch particles comprises, 1,8-diazacyclo laurylene 30g, 2-mercaptobenzimidazole zinc ZMBI 10g, chlorinated polyethylene rubber 40g, stearic acid 3g, pentaerythritol fatty ester 10g, ethylene-vinyl acetate copolymer EVM1g, Tritolyl Phosphate TCP5g and epoxidized fatty acid 1g.
Pentaerythritol fatty ester described in the present embodiment is pentaerythritol tetrastearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 40 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 40 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:100 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S8.
Embodiment 9
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, and the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 30g, chlorinated polyethylene rubber 70g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 10g, 2-thiol group tolimidazole zinc ZMMBI 20g, chlorinated polyethylene rubber 70g.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 100 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 100 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:1 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S9.
Embodiment 10
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione 25g, chlorinated polyethylene rubber 70g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM1g, dioctyl azelate DOZ 0.5g and dioctyl phthalate (DOP) DOP 0.5g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo 10g, 2-mercaptobenzimidazole MBI 15g, chlorinated polyethylene rubber 70g, stearic acid 1g, pentaerythritol fatty ester 1g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM1g, dioctyl azelate DOZ 0.5g and dioctyl phthalate (DOP) DOP 0.5g.
Pentaerythritol fatty ester described in the present embodiment is tetramethylolmethane tristearate.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 1:40 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S10.
Embodiment 11
Vulcanization accelerator in the present embodiment comprises pre-dispersed main body masterbatch particles and pre-dispersed part masterbatch particles, the raw material wherein preparing pre-dispersed main body masterbatch particles comprises, 3-methyl-2-thiazole thione (pale powder, first fusing point >=60 DEG C, screenings (63 μm)≤0.5%) 80g, chlorinated polyethylene rubber 8g, stearic acid (rubber industry grade, fusing point is 58 DEG C) 2g, pentaerythritol fatty ester 4g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM1g and liquid polarity softening agent DOA (Hazen colourity≤40, refractive index is 1.4470-1.4480) 4g.
The raw material preparing pre-dispersed part masterbatch particles comprises, diazabicylo (yellow transparent liquid, hydroxyl value is 0mgKOH/g, 25 DEG C of density are 1.04g/cm3) 50g, 2-thiol group tolimidazole MMBI (pale powder, density 1.25, fusing point 273 DEG C, weight loss on heating≤0.50%, ash content≤0.50%) 38g, chlorinated polyethylene rubber 10g, stearic acid (rubber industry grade, fusing point is 58 DEG C) 3g, pentaerythritol fatty ester 2g, ethylene-vinyl acetate copolymer EVA1g, ethylene-vinyl acetate copolymer EVM2g and liquid polarity softening agent DOA (Hazen colourity≤40, refractive index is 1.4470-1.4480) 2g.
Pentaerythritol fatty ester described in the present embodiment is the tetramethylolmethane tristearate of mass ratio 1:1 and the mixture of pentaerythritol tetrastearate formation.
The preparation method of the vulcanization accelerator masterbatch particles in the present embodiment is,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) be that 0.75:1.2 mixes by the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles with mass ratio, obtain described vulcanization accelerator composition S11.
Evaluation Example
The vulcanization accelerator composition 1.95g (0.75g pre-dispersed main body masterbatch particles and the pre-dispersed part masterbatch particles of 1.20g) that pre-dispersed main body masterbatch particles 0.75gETU, 0.75g embodiment 11 prepared respectively, embodiment 11 prepare joins in 201.5g chloroprene rubber finished composition, and three formula molded vulcanizations obtain cross-linked rubber.Wherein chloroprene rubber finished composition formula is chloroprene rubber 100g, 50g carbon black N550,20g calcinated argil, 20g softening agent DINP, 1g low molecular weight polyethylene, 1g octylated diphenylamine ODPA, 0.5g stearic acid, 9g vulcanizing agent.The performance data of above-mentioned vulcanization system and cross-linked rubber is as shown in table 1 below after measured; During vulcanization accelerator 1.95g in addition in Example 1-10, its cured properties of 170 DEG C × 10min is as shown in table 2.
Table 1
As can be seen from Table 1, when adopting different vulcanization accelerator, the tensile strength of the cross-linked rubber before aging is substantially identical, but after aging, the carcinogenic cross-linked rubber tensile strength change of filling a prescription with the ETU of toxicity of tradition is tending towards declining, and the stretching strength retentivity of the cross-linked rubber of the pre-dispersed main body masterbatch particles of S11 and S11 is higher.Illustrate that its heat-resistant aging improves.Also can find out from the data of compression set in 70 DEG C × 7 days in addition, S11 gives the compression set performance that cross-linked rubber improves, in table 1, data S11 (a) row refer to pre-dispersed for the 0.75g in embodiment 11 main body masterbatch particles and the pre-dispersed part masterbatch particles of 1.20g not to mix in addition, added in finished composition the performance data obtaining cross-linked rubber respectively, itself and S11 arrange and first mix that to add in finished composition the performance data obtaining cross-linked rubber more identical, show that two kinds of masterbatch particles can first mix by the promotor combination of the application to add again, also can add respectively.
Table 2
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (16)
1. a vulcanization accelerator composition, is characterized in that, comprises pre-dispersed main body masterbatch particles, is 100 mass parts to prepare the raw material of described pre-dispersed main body masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material,
3-methyl-2-thiazole thione 10 ~ 90 mass parts,
Rubber 5 ~ 90 mass parts.
2. vulcanization accelerator composition according to claim 1, is characterized in that, the raw material of described pre-dispersed main body masterbatch particles also comprises,
Stearic acid 1 ~ 10 mass parts,
Pentaerythritol fatty ester 1 ~ 10 mass parts,
Ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 part,
Liquid polarity softening agent 1 ~ 10 mass parts.
3. vulcanization accelerator composition according to claim 1 and 2, is characterized in that, also comprises pre-dispersed part masterbatch particles, is 100 mass parts to prepare the raw material of described pre-dispersed part masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material,
Ligand compound 10-90 mass parts, rubber 5 ~ 90 mass parts, described ligand compound is mass ratio is the organic amine compound of 1:9-9:1 and the mixture of benzimidazole compound formation.
4. vulcanization accelerator composition according to claim 3, is characterized in that, described organic amine compound is diazabicylo or 1,8-diazacyclo laurylene.
5. the vulcanization accelerator composition according to claim 3 or 4, it is characterized in that, described benzimidazole compound is 2-mercaptobenzimidazole MBI, 2-mercaptobenzimidazole zinc ZMBI, 2-thiol group tolimidazole MMBI or 2-thiol group tolimidazole zinc ZMMBI.
6., according to the arbitrary described vulcanization accelerator composition of claim 3-5, it is characterized in that, the raw material of described pre-dispersed part masterbatch particles also comprises,
Stearic acid 1 ~ 10 mass parts,
Pentaerythritol fatty ester 1 ~ 10 mass parts,
Ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts,
Liquid polarity softening agent 1 ~ 10 mass parts.
7. vulcanization accelerator composition according to claim 6, is characterized in that, is 100 mass parts to prepare the raw material of described pre-dispersed part masterbatch particles, and described pre-dispersed main body masterbatch particles comprises following raw material,
Organic amine compound 10-60 mass parts,
Benzimidazole compound 10-50 mass parts,
Rubber 5 ~ 90 mass parts,
Stearic acid 1 ~ 10 mass parts,
Ethylene-vinyl acetate copolymer EVA and/or ethylene-vinyl acetate copolymer EVM 1-10 mass parts,
Pentaerythritol fatty ester 1 ~ 10 mass parts,
Liquid polarity softening agent 1 ~ 10 mass parts.
8. according to the arbitrary described vulcanization accelerator composition of claim 2-7, it is characterized in that, described rubber is polyacrylic rubber ACM, ethylene-acrylate copolymers rubber AEM, urethanes PUR, isoprene-isobutylene rubber IIR, chlorinated butyl rubber CIIR, brominated butyl rubber BIIR, cis-1,4-polybutadiene rubber BR, homopolymerization chlorohydrin rubber CO, copolymerization chlorohydrin rubber ECO, chloroprene rubber CR, chlorinated polyethylene rubber CPE, chlorosulfonated polyethylene rubber CSM, ethylene propylene rubber EPM, terpolymer EP rubber EPDM, viton FPM, trifluoropropyl siloxane FVMQ, polyisoprene rubber IR, Natural rubber, styrene butadiene rubber sbr, one or more in paracril NBR.
9. vulcanization accelerator composition according to claim 8, is characterized in that, described rubber is chlorinated polyethylene rubber, and its cl content is 30 ~ 45wt%, mooney viscosity ML125 DEG C of (1+4)=45 ~ 85.
10., according to the arbitrary described vulcanization accelerator composition of claim 2-8, it is characterized in that, described pentaerythritol fatty ester is tetramethylolmethane tristearate and/or pentaerythritol tetrastearate.
11. according to the arbitrary described vulcanization accelerator composition of claim 2-10, it is characterized in that, described liquid polarity softening agent is one or more in dibutyl phthalate DBP, dioctyl phthalate (DOP) DOP, diisononyl phthalate DINP, Octyl adipate DOA, dioctyl azelate DOZ, dioctyl sebacate DOS, Tritolyl Phosphate TCP, liquid chlorinated paraffin and epoxidized fatty acid.
12. according to the arbitrary described vulcanization accelerator composition of claim 3-11, and it is characterized in that, the mass ratio of described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles is 1:100-100:1.
The preparation method of 13. 1 kinds of arbitrary described vulcanization accelerator compositions of claim 1-12, comprises,
(1) by the raw material mixing of the described pre-dispersed main body masterbatch particles of preparation, and mixing at 35-100 DEG C, and extruding pelletization obtains described pre-dispersed main body masterbatch particles, for subsequent use;
(2) described organic amine compound is mixed with described benzimidazole compound, stir and obtain part powder, described part powder other raw material with the described pre-dispersed part masterbatch particles of preparation is mixed, and it is mixing at 35-100 DEG C, extruding pelletization obtains described pre-dispersed part masterbatch particles, for subsequent use;
(3) the described pre-dispersed main body masterbatch particles prepared and described pre-dispersed part masterbatch particles are mixed, obtain described vulcanization accelerator composition.
The preparation method of 14. vulcanization accelerator compositions according to claim 13, is characterized in that,
The melting temperature of described step (1) and step (2) is 35-55 DEG C.
The arbitrary described vulcanization accelerator composition of 15. claim 1-12 is promoting the application in the vulcanization of rubber.
16. vulcanization accelerator compositions according to claim 15 are promoting the application in the vulcanization of rubber; it is characterized in that; respectively described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles are joined in finished composition system, or join after described pre-dispersed main body masterbatch particles and described pre-dispersed part masterbatch particles mixing in finished composition system.
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