CN105713304B - Pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide and preparation method thereof - Google Patents
Pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide and preparation method thereof Download PDFInfo
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- CN105713304B CN105713304B CN201610249499.9A CN201610249499A CN105713304B CN 105713304 B CN105713304 B CN 105713304B CN 201610249499 A CN201610249499 A CN 201610249499A CN 105713304 B CN105713304 B CN 105713304B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
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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
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide disclosed by the invention can effectively solve the TBTD of liquid form in direct be kneaded, with the slow problem of mixing caused by the polarity difference of rubber；Flow behavior is good in rubber after the masterbatch particles dispensing, it charging rate can add faster, and inclusion quantity is high, even if in the case of with rubber polarity difference, also can combine closely in time with rubber, preferable dispersiveness can be kept under different shearing forces, in addition, the masterbatch particles can also further improve the dispersiveness and mobility of rubber active ingredient, improve its compatibility with rubber, reduce the additive amount of other auxiliary agents, improve rubber production efficiency, and reduce dust pollution, improve the working environment of workers, also there is the rejection rate for reducing rubber simultaneously；The masterbatch particles that the method for the present invention is prepared can be effectively retained original activity of TBTD, not lump at room temperature, and convenient for weighing, the mixing ingredient for follow-up rubber provides great convenience.
Description
Technical field
The present invention relates to rubber chemicals and its preparing technical fields, are specifically a kind of rubber accelerator curing tetrabutyl autumn
Blue pre-dispersed masterbatch particles of nurse and preparation method thereof.
Background technology
Rubber accelerator tetrabutylthiuram disulfide（TBTD）, it is a kind of thuriam acceserator, is in dun under room temperature
Color oily liquids dissolves in most organic solvents, but not soluble in water.TBTD can be used as thiofide, also can be used as sulphur
Agent, effective sulfur content 7.5%.TBTD no bloomings in sizing material, do not pollute, available for the manufacture inner tube of a tyre, rubber overshoes, adhesive plaster, industry
Product etc..
Auxiliary agent form is divided into solid-state and liquid needed for compounding rubber.For from form, TBTD is a kind of liquid flux.
Liquid flux is in input mixer and rubber mixing process, since itself and some rubber cause to be kneaded there are the difference of polarity
It is relatively slow, and the mixing in mixer needs to carry out under relatively low shearing force, and because liquid flux is mixed into rubber
Disperse relatively slow, poor fluidity after glue, cause that the compounding rubber cycle is long, efficiency is low.
The content of the invention
The technical problems to be solved by the invention are：In view of the deficiencies of the prior art, a kind of two sulphur of rubber accelerator is provided
Change pre-dispersed masterbatch particles of tetrabutyl thiuram and preparation method thereof.
Technical solution is used by the present invention solves above-mentioned technical problem：Rubber accelerator tetrabutylthiuram disulfide
Pre-dispersed masterbatch particles, are counted in parts by weight, and the composition of the masterbatch particles is：50~65 parts of tetrabutylthiuram disulfide, without airborne
20~25 parts of body, 12~19 parts of rubber matrix, 1~3 part of technical white oil, 2~6 parts of rubber oil.
Preferably, the rubber matrix by ethylene propylene diene rubber, bibasic ethylene propylene rubber, EVA resin, stearic acid and oneself
Adipate forms, the ethylene propylene diene rubber, bibasic ethylene propylene rubber, EVA resin, stearic acid and dioctyl adipate
Weight ratio is（4~8）：（3~7）：（1~3）：（1~3）：（1~3）.Further, count in parts by weight, the group of the masterbatch particles
Become：55 parts of tetrabutylthiuram disulfide, 23 parts of inorganic carrier, 6 parts of ethylene propylene diene rubber, 6 parts of bibasic ethylene propylene rubber, EVA
1 part of resin, 1 part of stearic acid, 2 parts of dioctyl adipate, 2 parts of technical white oil, 4 parts of rubber oil.
Preferably, the rubber matrix is made of butadiene-styrene rubber, stearic acid and zinc stearate, the butylbenzene rubber
The weight ratio of glue, stearic acid and zinc stearate is（10~14）：1：（1~3）.Further, count in parts by weight, the masterbatch particles
Composition be：55 parts of tetrabutylthiuram disulfide, 24 parts of inorganic carrier, 12 parts of butadiene-styrene rubber, 1 part of stearic acid, zinc stearate 2
Part, 2 parts of technical white oil, 4 parts of rubber oil.
Preferably, the inorganic carrier is powdered inorganic carrier, the particle size range of the inorganic carrier for 5~
40 microns.Further, the inorganic carrier is at least one in white carbon, carbon black, calcium carbonate, silica and clay
Kind.
The preparation method of the above-mentioned pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide, comprises the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using inorganic carrier as carrier, the pre- of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid
Mixed object；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, is kneaded 8~15 points
It discharges after clock, 60~80 DEG C of drop temperature obtains sizing material；
（5）Host given rotating speed is controlled as 95~105 r/min, by step（4）In obtained sizing material feeding to extruder,
Feeding rotating speed is 15~25 r/min, and the temperature control region of the extruder is divided into seven sections from feed inlet to discharge port, wherein the
One section of temperature is 25~35 DEG C, and the temperature of second segment to the 7th section is 35~45 DEG C, finally extrudes to obtain rubber accelerator
The pre-dispersed masterbatch particles of tetrabutylthiuram disulfide.
Compared with prior art, the advantage of the invention is that：
（1）The present invention by the tetrabutylthiuram disulfide of liquid and inorganic carrier by being mixed to get the pre- of solid-state form
Mixed object, then the pre-composition and remaining raw material are added in mixer by several times, it is kneaded in mixer and extrudes in an extruder
To the pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide, the curing tetrabutyl autumn of liquid form can be effectively solved
Blue nurse is when being directly kneaded, with the slow problem of mixing caused by the polarity difference of rubber；
（2）The masterbatch particles that the method for the present invention is prepared can be effectively retained original activity of tetrabutylthiuram disulfide,
It does not lump at room temperature, convenient for weighing, the mixing ingredient for follow-up rubber provides great convenience；
（3）Flow behavior is good in rubber after the pre-dispersed masterbatch particles dispensing of the present invention, charging rate can add faster,
And the masterbatch particles inclusion quantity is high, even if in the case of with rubber polarity difference, can also combine closely in time with rubber,
Preferable dispersiveness can be kept under different shearing forces, in addition, the masterbatch particles can also further improve rubber active ingredient
Dispersiveness and mobility, improve the compatibility of active ingredient and rubber, reduce the additive amount of other auxiliary agents, shorten compounding rubber
Cycle improves melting effect, improves rubber production efficiency, and reduces dust pollution, improves the working environment of workers, while also has
Reduce the effect of the rejection rate of rubber；
（4）After pre-dispersed masterbatch particles are made by the method for the present invention, tetrabutylthiuram disulfide is wrapped in rubber-based
In body, the packaging of the solid product, transport and very easy to use.
Specific embodiment
The present invention is described in further detail with reference to embodiments.
The pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide of embodiment one, are counted, the mother in parts by weight
The composition of micelle is：55 parts of tetrabutylthiuram disulfide, 23 parts of white carbon, 6 parts of ethylene propylene diene rubber, bibasic ethylene propylene rubber 6
Part, 1 part of EVA resin, 1 part of stearic acid, 2 parts of dioctyl adipate, 2 parts of technical white oil, 4 parts of rubber oil.The preparation of the masterbatch particles
Method comprises the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using white carbon as carrier, the premix of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid
Object；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, is kneaded after ten minutes
Discharging, 60~80 DEG C of drop temperature obtain sizing material；
（5）Host given rotating speed is controlled as 100 r/min, by step（4）In obtained sizing material feeding to extruder, feeding
Rotating speed is 20 r/min, and the temperature control region of the extruder is divided into seven sections, the wherein temperature of first segment from feed inlet to discharge port
It spends for 30 DEG C, the temperature of second segment to the 7th section is 40 DEG C, finally extrudes to obtain the rubber accelerator curing of embodiment one
The pre-dispersed masterbatch particles TBTD-55/EPDM of tetrabutyl thiuram.The appearance of the pre-dispersed masterbatch particles is estimated as celadon, after testing,
The total sulfur content of the masterbatch particles is 17.1 %, and density at 20 DEG C is 1.14 g/cm3, 50 DEG C of Mooney viscosity ML（1+4）For
52.8。
The pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide of embodiment two, are counted, the mother in parts by weight
The composition of micelle is：55 parts of tetrabutylthiuram disulfide, 24 parts of white carbon, 12 parts of butadiene-styrene rubber, 1 part of stearic acid, stearic acid
2 parts of zinc, 2 parts of technical white oil, 4 parts of rubber oil.The preparation method of the masterbatch particles, comprises the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using white carbon as carrier, the premix of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid
Object；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, after being kneaded 12 minutes
Discharging, 60~80 DEG C of drop temperature obtain sizing material；
（5）Host given rotating speed is controlled as 105 r/min, by step（4）In obtained sizing material feeding to extruder, feeding
Rotating speed is 18 r/min, and the temperature control region of the extruder is divided into seven sections, the wherein temperature of first segment from feed inlet to discharge port
It spends for 32 DEG C, the temperature of second segment to the 7th section is 43 DEG C, finally extrudes to obtain the rubber accelerator curing of embodiment two
The pre-dispersed masterbatch particles TBTD-55/SBR of tetrabutyl thiuram.The appearance of the pre-dispersed masterbatch particles is estimated as celadon, after testing,
The total sulfur content of the masterbatch particles is 16.6 %, and density at 20 DEG C is 1.16 g/cm3, 50 DEG C of Mooney viscosity ML（1+4）For
52.0。
The pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide of embodiment three, are counted, the mother in parts by weight
The composition of micelle is：56 parts of tetrabutylthiuram disulfide, 25 parts of silica, 5.5 parts of ethylene propylene diene rubber, the third rubber of binary second
5.5 parts of glue, 1 part of EVA resin, 1 part of stearic acid, 1.5 parts of dioctyl adipate, 1 part of technical white oil, 3.5 parts of rubber oil.The rubber master batch
The preparation method of grain, comprises the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using silica as carrier, the pre- of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid
Mixed object；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, after being kneaded 14 minutes
Discharging, 60~80 DEG C of drop temperature obtain sizing material；
（5）Host given rotating speed is controlled as 98 r/min, by step（4）In obtained sizing material feeding to extruder, feeding
Rotating speed is 21 r/min, and the temperature control region of the extruder is divided into seven sections, the wherein temperature of first segment from feed inlet to discharge port
It spends for 28 DEG C, the temperature of second segment to the 7th section is 38 DEG C, finally extrudes to obtain the rubber accelerator curing of embodiment three
The pre-dispersed masterbatch particles TBTD-55/EPDM of tetrabutyl thiuram.The appearance of the pre-dispersed masterbatch particles is estimated as celadon, after testing,
The total sulfur content of the masterbatch particles is 17.3 %, and density at 20 DEG C is 1.15 g/cm3, 50 DEG C of Mooney viscosity ML（1+4）For
53.3。
The pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide of example IV, are counted, the mother in parts by weight
The composition of micelle is：57 parts of tetrabutylthiuram disulfide, 22 parts of calcium carbonate, 13 parts of butadiene-styrene rubber, 1 part of stearic acid, stearic acid
3 parts of zinc, 1 part of technical white oil, 3 parts of rubber oil.The preparation method of the masterbatch particles, comprises the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using calcium carbonate as carrier, the premix of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid
Object；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, after being kneaded 9 minutes
Discharging, 60~80 DEG C of drop temperature obtain sizing material；
（5）Host given rotating speed is controlled as 102 r/min, by step（4）In obtained sizing material feeding to extruder, feeding
Rotating speed is 22 r/min, and the temperature control region of the extruder is divided into seven sections, the wherein temperature of first segment from feed inlet to discharge port
It spends for 30 DEG C, the temperature of second segment to the 7th section is 42 DEG C, finally extrudes to obtain the rubber accelerator curing of example IV
The pre-dispersed masterbatch particles TBTD-55/SBR of tetrabutyl thiuram.The appearance of the pre-dispersed masterbatch particles is estimated as celadon, after testing,
The total sulfur content of the masterbatch particles is 17.4 %, and density at 20 DEG C is 1.18 g/cm3, 50 DEG C of Mooney viscosity ML（1+4）For
52.9。
In embodiments above, the detailed process for preparing sheet rubber matrix is：System is weighed first, in accordance with proportion speed
Each raw material needed for standby rubber matrix, and ethylene propylene diene rubber and bibasic ethylene propylene rubber will be removed（Or butadiene-styrene rubber）Preparation in addition
Other raw materials needed for rubber matrix are divided into three parts；Again by ethylene propylene diene rubber and bibasic ethylene propylene rubber（Or butadiene-styrene rubber）It puts
In the mixer for entering 75L, it is kneaded 2~5 minutes；Then 1/3 other raw materials are added in the mixer, are kneaded 3~5 minutes；
1/3 other raw materials are added in the mixer afterwards, temperature is kneaded into mixer and rises to 80 ± 2 DEG C, then to mixer
Other raw materials of middle addition remaining 1/3, are kneaded to 95 ± 2 DEG C, dumping obtains rubber matrix sizing material；Finally by rubber matrix
Sizing material on a mill the thin logical glue bottom sheet of leading three times of room temperature to get to sheet rubber matrix.
Claims (4)
1. the pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide, it is characterised in that：It counts in parts by weight, the rubber master batch
Grain composition be：50~65 parts of tetrabutylthiuram disulfide, 20~25 parts of inorganic carrier, 12~19 parts of rubber matrix, industry
1~3 part of white oil, 2~6 parts of rubber oil；The inorganic carrier be powdered inorganic carrier, the grain size model of the inorganic carrier
It encloses for 5~40 microns, the inorganic carrier is at least one of carbon black, calcium carbonate, silica and clay；The rubber
Matrix body is made of ethylene propylene diene rubber, bibasic ethylene propylene rubber, EVA resin, stearic acid and dioctyl adipate, the ternary
EP rubbers, bibasic ethylene propylene rubber, EVA resin, the weight ratio of stearic acid and dioctyl adipate are（4~8）：（3~7）：（1
~3）：（1~3）：（1~3）, alternatively, the rubber matrix is made of butadiene-styrene rubber, stearic acid and zinc stearate, it is described
The weight ratio of butadiene-styrene rubber, stearic acid and zinc stearate is（10~14）：1：（1~3）.
2. the pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide according to claim 1, it is characterised in that：
It counts in parts by weight, the composition of the masterbatch particles is：55 parts of tetrabutylthiuram disulfide, 23 parts of inorganic carrier, ethylene-propylene-diene monomer
6 parts of glue, 6 parts of bibasic ethylene propylene rubber, 1 part of EVA resin, 1 part of stearic acid, 2 parts of dioctyl adipate, 2 parts of technical white oil, rubber oil
4 parts.
3. the pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide according to claim 1, it is characterised in that：
It counts in parts by weight, the composition of the masterbatch particles is：55 parts of tetrabutylthiuram disulfide, 24 parts of inorganic carrier, butadiene-styrene rubber 12
Part, 1 part of stearic acid, 2 parts of zinc stearate, 2 parts of technical white oil, 4 parts of rubber oil.
4. the system of the pre-dispersed masterbatch particles of rubber accelerator tetrabutylthiuram disulfide according to any one of claims 1 to 3
Preparation Method, which is characterized in that comprise the following steps：
（1）Prepare sheet rubber matrix；
（2）It is weighed according to proportion speed and prepares each raw material needed for masterbatch particles；
（3）Using inorganic carrier as carrier, the pre-composition of solid-state form is mixed to get with the tetrabutylthiuram disulfide of liquid；
（4）Pre-composition and remaining raw material are fed intake in three times respectively and added in mixer, is uniformly mixed, after being kneaded 8~15 minutes
Discharging, 60~80 DEG C of drop temperature obtain sizing material；
（5）Host given rotating speed is controlled as 95~105 r/min, by step（4）In obtained sizing material feeding to extruder, feeding
Rotating speed is 15~25 r/min, and the temperature control region of the extruder is divided into seven sections, wherein first segment from feed inlet to discharge port
Temperature for 25~35 DEG C, the temperature of second segment to the 7th section is 35~45 DEG C, finally extrudes to obtain two sulphur of rubber accelerator
Change the pre-dispersed masterbatch particles of tetrabutyl thiuram.
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| CN108976522A (en) * | 2018-07-11 | 2018-12-11 | 宁波艾克姆新材料有限公司 | Pre-dispersed masterbatch particles of 2- mercaptan ylmethylbenzimidazole and preparation method thereof |
| CN109181044A (en) * | 2018-07-11 | 2019-01-11 | 宁波艾克姆新材料有限公司 | Pre-dispersed masterbatch particles of rubber antioxidant ZMMBI and preparation method thereof |
| CN109627536B (en) * | 2018-12-26 | 2021-02-12 | 昆山亚特曼新材料科技有限公司 | Pre-dispersed masterbatch particle and processing method |
| CN112251033A (en) * | 2020-07-30 | 2021-01-22 | 珠海科茂威新材料有限公司 | High-activity TBzTD promoter master colloidal particle and preparation method thereof |
| CN113817271B (en) * | 2021-10-26 | 2022-08-09 | 江苏麒祥高新材料有限公司 | Dihydrazide pre-dispersed masterbatch particle composition and preparation method thereof |
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| CN102134354A (en) * | 2011-04-22 | 2011-07-27 | 连云港连连化学有限公司 | Pre-dispersing masterbatch particle of liquid rubber chemicals and preparation method thereof |
| CN105111539A (en) * | 2015-09-09 | 2015-12-02 | 宁波硫华聚合物有限公司 | Environment-friendly rubber aid TBzTD pre-dispersed masterbatch and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102134354A (en) * | 2011-04-22 | 2011-07-27 | 连云港连连化学有限公司 | Pre-dispersing masterbatch particle of liquid rubber chemicals and preparation method thereof |
| CN105111539A (en) * | 2015-09-09 | 2015-12-02 | 宁波硫华聚合物有限公司 | Environment-friendly rubber aid TBzTD pre-dispersed masterbatch and preparation method thereof |
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