CN103554684A - Masterbatch particle composition of vulcanization accelerator 2,2'-dibenzothiazole disulfide (MBTS) for rubber and preparation method thereof - Google Patents
Masterbatch particle composition of vulcanization accelerator 2,2'-dibenzothiazole disulfide (MBTS) for rubber and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a masterbatch particle composition of vulcanization accelerator 2,2'-dibenzothiazole disulfide (MBTS) for rubber and a preparation method thereof. The composition comprises the following components in parts by weight: 70-80 parts of accelerator MBTS, 8-21 parts of carriers, 3-5 parts of stearic acid and 6-9 parts of white oil; the preparation method comprises the following steps: pre-heating an internal mixer to 50-60 DEG C, putting the carriers, MBTS, stearic acid and white oil into the internal mixer for internal mixing, and slicing and pelleting after mixing uniformly. According to the masterbatch particle prepared by the method, the traditional mode that the carrier is firstly prepared at a higher temperature (not less than 80 DEG C) and then the masterbatch particle is prepared at a lower temperature (50-60 DEG C) is changed, the masterbatch particle can be directly prepared at the low temperature in one step, so that the method is convenient to operate, problems of dust, mixing rate and the like of the auxiliary powder in the mixing process are improved, and meanwhile the production efficiency of the masterbatch particle is greatly improved.
Description
Technical field
The present invention relates to rubber ingredients composition, relate more specifically to the preparation of pre-dispersed type rubber vulcanization accelerator dibenzothiazyl disulfide (being called for short MBTS) masterbatch particles, this product is mainly used in Vulcanization Process of Rubber.
Background technology
Accelerator M BTS is the universal promotor of a kind of rubber, is the universal promotor of natural rubber, synthetic rubber, reclaimed rubber, mainly for the manufacture of tire, the inner tube of a tyre, adhesive tape, rubber overshoes and general industry goods.
Traditional rubber ingredients mostly are powdery chemical, although can bring great benefit for rubber item and processing thereof, but also there are many weak points: the one, powdery auxiliary agent is poorer than pre-dispersed rubber ingredients master batch with the consistency of rubber, glue master batch goods are more difficult is relatively evenly dispersed in rubber, therefore, the rubber item of employing powdery auxiliary agent can be lower than adopting glue master batch goods rubber item in quality; The 2nd, can cause more energy loss.While adopting rubber powder auxiliary agent, in order being uniformly dispersed, in actually operating, often to adopt and extend mixing time, improve the ways such as melting temperature, this can bring more energy waste and the problem such as excessively crosslinked; The 3rd, be not easy to automatically control dosage.Due to the physical adsorption characteristic of powdery auxiliary agent, in adding the process of rubber item, be easily adsorbed on vessel wall, be not easy to automatically control input; The 4th, it is larger than glue master batch class rubber ingredients that transportation stores difficulty.The easy moisture absorption of powdery auxiliary agent, storage requirement is higher than glue master batch shape auxiliary agent, and due to its pulverous feature, transportation cost is also higher than glue master batch auxiliary agent.
Pre-dispersed rubber ingredients master batch is a class new type rubber processing aid of developing by " green chemical industry " new ideas, and its advantage is under lower melting temperature, and this system also has lower viscosity and low shearing rate, thereby is easy to disperse.
Adopt pre-dispersed type rubber ingredients master batch to replace common flour body rubber processing aid, can improve dispersiveness, improve the quality of products, convenient use, reduces melting temperature, is conducive to energy-conservationly, and convenient storage and automatic gauge etc., be the rubber ingredients developing direction in future.External rubber industry has started to adopt pre-dispersed rubber ingredients master batch.Therefore rubber accelerator is prepared into masterbatch particles China's rubber ingredients are moved towards internationalization, widen market, especially to adapting to Rubber Chemicals Industries trend, advancing the production that cleans of China's Rubber Chemicals Industries to have important strategic importance and necessity.
Summary of the invention
The object of the present invention is to provide the pre-dispersed masterbatch particles composition of a kind of accelerator M BTS and preparation method, masterbatch particles prepared by the method has changed the first comparatively high temps of traditional needs (being not less than 80 ℃) and has prepared carrier, and then under lesser temps (50～60 ℃), prepare the mode of masterbatch particles, can directly in low temperature one step, prepare masterbatch particles, this method is easy to operate, has improved the production efficiency that has greatly improved masterbatch particles in the problems such as dust in mixing process of powder auxiliary agent, mixing rate.
For achieving the above object, the present invention is realized by following technical proposals:
The pre-dispersed masterbatch particles of S, component and mass fraction are as follows:
The pre-dispersed masterbatch particles of S, described carrier can mix for single variety or the multiple glue of ethylene-propylene diene copolymer, binary second the third glue, butadiene-styrene rubber or butadiene-acrylonitrile rubber;
Described solid support material is preferably ethylene-propylene diene copolymer and the mixture of binary second the third glue or the mixture of ethylene-propylene diene copolymer and butadiene-styrene rubber; Ethylene-propylene diene copolymer: the ratio of quality and the number of copies of binary second the third glue is (1～4): 1; Ethylene-propylene diene copolymer: the quality of butadiene-styrene rubber is 1:(1～4 than umber).The preparation method of the pre-dispersed masterbatch particles of accelerant MBT S of the present invention, comprises the following steps:
Banbury mixer is preheated to 50～60 ℃, carrier, MBTS, stearic acid and white oil is required to drop in Banbury mixer according to above-mentioned umber and carry out banburying, lower sheet, granulation after banburying evenly.
The invention has the advantages that: the method is simple to operate, solved in the use procedure of traditional accelerant MBT S powder dust large, disperse the problems such as inhomogeneous, and simplified masterbatch particles preparation process, increased in use procedure the consistency with rubber, reduce mixing time, improved efficiency.
Embodiment
Embodiment 1:
Banbury mixer is preheated to 50 ℃, 9 parts of MBTS80 parts, 1.6 parts of ethylene-propylene diene copolymers, 6.4 parts of butadiene-styrene rubbers, 3 parts of stearic acid, white oil are added and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles A.
Embodiment 2:
Banbury mixer is preheated to 60 ℃, 8 parts of MBTS80 parts, 1.6 parts of ethylene-propylene diene copolymers, 6.4 parts of butadiene-styrene rubbers, 4 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles B.
Embodiment 3:
Banbury mixer is preheated to 55 ℃, 7 parts of MBTS77 parts, 1.6 parts of ethylene-propylene diene copolymers, 6.4 parts of butadiene-styrene rubbers, 5 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles C.
Embodiment 4
Banbury mixer is preheated to 50 ℃, 6 parts of MBTS77 parts, 2.2 parts of ethylene-propylene diene copolymers, 8.8 parts of butadiene-styrene rubbers, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles D.
Embodiment 5
Banbury mixer is preheated to 55 ℃, 9 parts of MBTS77 parts, 3.3 parts of ethylene-propylene diene copolymers, 7.7 parts of butadiene-styrene rubbers, 4 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles E.
Embodiment 6
Banbury mixer is preheated to 60 ℃, 8 parts of MBTS78 parts, 4.4 parts of ethylene-propylene diene copolymers, 6.6 parts of butadiene-styrene rubbers, 5 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles F.
Embodiment 7
Banbury mixer is preheated to 50 ℃, 7 parts of MBTS70 parts, 3 parts of ethylene-propylene diene copolymers, 7 parts of butadiene-styrene rubbers, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles G.
Embodiment 8
Banbury mixer is preheated to 55 ℃, 6 parts of MBTS70 parts, 4 parts of ethylene-propylene diene copolymers, 6 parts of butadiene-styrene rubbers, 4 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles H.
Embodiment 9
Banbury mixer is preheated to 60 ℃, 9 parts of MBTS77 parts, 5 parts of ethylene-propylene diene copolymers, 5 parts of butadiene-styrene rubbers, 5 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles I.
Embodiment 10:
Banbury mixer is preheated to 50 ℃, 8 parts of the third 1.6 parts of MBTS80 parts, 6.4 parts of ethylene-propylene diene copolymers, binary second, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles A1.
Embodiment 11:
Banbury mixer is preheated to 60 ℃, 7 parts of MBTS80 parts, 6.4 parts of ethylene-propylene diene copolymers, 1.6 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles B1.
Embodiment 12:
Banbury mixer is preheated to 55 ℃, 6 parts of MBTS80 parts, 6.4 parts of ethylene-propylene diene copolymers, 1.6 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles C1.
Embodiment 13:
Banbury mixer is preheated to 50 ℃, 9 parts of MBTS75 parts, 8.8 parts of ethylene-propylene diene copolymers, 2.2 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles D1.
Embodiment: 14:
Banbury mixer is preheated to 55 ℃, 8 parts of MBTS75 parts, 9.5 parts of ethylene-propylene diene copolymers, 4.1 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles E1.
Embodiment: 15:
Banbury mixer is preheated to 60 ℃, 7 parts of MBTS80 parts, 9 parts of ethylene-propylene diene copolymers, 6 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles F1.
Embodiment: 16:
Banbury mixer is preheated to 50 ℃, 6 parts of MBTS73 parts, 10.5 parts of ethylene-propylene diene copolymers, 4.5 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles G1.
Embodiment: 17:
Banbury mixer is preheated to 55 ℃, 9 parts of MBTS76 parts, 12.6 parts of ethylene-propylene diene copolymers, 8.4 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles H1.
Embodiment: 18:
Banbury mixer is preheated to 60 ℃, 8 parts of MBTS80 parts, 10.5 parts of ethylene-propylene diene copolymers, 10.5 parts, binary second the third glue, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles I1.
Embodiment: 19:
Banbury mixer is preheated to 50 ℃, 8 parts of MBTS80 parts, 15 parts, styrene-butadiene rubber(SBR), 4 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles A2.
Embodiment: 20:
Banbury mixer is preheated to 60 ℃, 8 parts of MBTS80 parts, 10 parts of ethylene-propylene diene copolymers, 3 parts of stearic acid, white oil are added successively and mixingly in Banbury mixer obtain lower, granulation after evenly and obtain masterbatch particles B2.
The masterbatch particles obtaining in above embodiment is brought into respectively and in rubber compounding, carried out quantitative measurement, and test result is in Table 1 and table 2:
Table 1 accelerant MBT S masterbatch particles and power applications performance comparison table
Table 2 accelerant MBT S masterbatch particles and power applications performance comparison table
Claims (5)
1. the pre-dispersed masterbatch particles composition of accelerator M BTS, is characterized in that component and mass fraction are as follows:
2. composition as claimed in claim 1, is characterized in that described carrier is that single variety or the multiple glue of ethylene-propylene diene copolymer, binary second the third glue, butadiene-styrene rubber or butadiene-acrylonitrile rubber mixes.
3. composition as claimed in claim 2, is characterized in that described mixed carrier is the mixture of ethylene-propylene diene copolymer and binary second the third glue, ethylene-propylene diene copolymer: the ratio of quality and the number of copies of binary second the third glue is (1～4): 1.
4. composition as claimed in claim 2, is characterized in that described mixed carrier is the mixture of ethylene-propylene diene copolymer and butadiene-styrene rubber; Ethylene-propylene diene copolymer: the quality of butadiene-styrene rubber is 1:(1～4 than umber).
5. the pre-dispersed masterbatch particles preparation method of the accelerator M BTS of claim 1, is characterized in that Banbury mixer to be preheated to 50～60 ℃, carrier, MBTS, stearic acid and white oil is dropped in Banbury mixer and carries out banburying, lower sheet, granulation after banburying evenly.
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| CN201310507836.6A CN103554684A (en) | 2013-10-24 | 2013-10-24 | Masterbatch particle composition of vulcanization accelerator 2,2'-dibenzothiazole disulfide (MBTS) for rubber and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987604A (en) * | 2015-07-16 | 2015-10-21 | 山东阳谷华泰化工股份有限公司 | Tetramethylthiuram disulfide pre-dispersed mother colloidal particle and preparation method thereof |
| CN104987603A (en) * | 2015-07-16 | 2015-10-21 | 山东阳谷华泰化工股份有限公司 | Zinc dimethyldithiocarbamate pre-dispersed mother colloidal particle and preparation method thereof |
| CN105837871A (en) * | 2016-05-23 | 2016-08-10 | 华南协同创新研究院 | Rubber accelerator and preparation method thereof |
| CN109251421A (en) * | 2018-07-11 | 2019-01-22 | 宁波艾克姆新材料有限公司 | Pre-dispersed masterbatch particles of MDB and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617937A (en) * | 2012-03-20 | 2012-08-01 | 珠海经济特区科茂橡塑材料有限公司 | Rubber additive pre-dispersion, preparation method thereof and method for preparing rubber additives |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617937A (en) * | 2012-03-20 | 2012-08-01 | 珠海经济特区科茂橡塑材料有限公司 | Rubber additive pre-dispersion, preparation method thereof and method for preparing rubber additives |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987604A (en) * | 2015-07-16 | 2015-10-21 | 山东阳谷华泰化工股份有限公司 | Tetramethylthiuram disulfide pre-dispersed mother colloidal particle and preparation method thereof |
| CN104987603A (en) * | 2015-07-16 | 2015-10-21 | 山东阳谷华泰化工股份有限公司 | Zinc dimethyldithiocarbamate pre-dispersed mother colloidal particle and preparation method thereof |
| CN105837871A (en) * | 2016-05-23 | 2016-08-10 | 华南协同创新研究院 | Rubber accelerator and preparation method thereof |
| CN109251421A (en) * | 2018-07-11 | 2019-01-22 | 宁波艾克姆新材料有限公司 | Pre-dispersed masterbatch particles of MDB and preparation method thereof |
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Application publication date: 20140205 |