CN103554559A - Preparation method of hydroxyethyl methacrylate rubber graft-modified white carbon black-reinforced natural rubber composite material - Google Patents
Preparation method of hydroxyethyl methacrylate rubber graft-modified white carbon black-reinforced natural rubber composite material Download PDFInfo
- Publication number
- CN103554559A CN103554559A CN201310518333.9A CN201310518333A CN103554559A CN 103554559 A CN103554559 A CN 103554559A CN 201310518333 A CN201310518333 A CN 201310518333A CN 103554559 A CN103554559 A CN 103554559A
- Authority
- CN
- China
- Prior art keywords
- carbon black
- rubber
- white carbon
- hydroxyethyl methylacrylate
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a preparation method of a hydroxyethyl methacrylate rubber graft-modified white carbon black-reinforced natural rubber composite material. The method concretely comprises the following steps: adding white carbon black, a proper coupling agent, an anionic surfactant and milky hydroxyethyl methacrylate rubber to deionized water, so as to prepare white carbon black emulsion dispersion by adopting mixing and ultrasonic dispersing manners; simultaneously, stabilizing the milky natural rubber by adopting a proper nonionic surfactant and then evenly mixing the white carbon black emulsion dispersion into the milky natural rubber; dropwise adding an initiating and crosslinking agent, so as to obtain a hydroxyethyl methacrylate rubber graft-modified white carbon black-natural rubber composite material in a latex state; treating the composite materials by standard conventional processing technologies of rubber in China, such as solidifying, tabletting, washing, drying and the like to obtain the hydroxyethyl methacrylate rubber graft-modified white carbon black-natural rubber composite material in a dry glue state. The white carbon black-natural rubber composite material prepared by the method disclosed by the invention is good in performance.
Description
Technical field
The present invention relates to the preparation method of native rubber composite material, particularly a kind of hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black strengthens the preparation method of native rubber composite material, belongs to elastomeric material production technical field.
Background technology
Because free volume is large, Intermolecular Forces is little, and crystallizing power is poor, if most rubber without reinforcement, its over-all properties cannot reach application purpose.In order to improve the tensile strength of rubber, the performances such as tear strength and wear resistant, improve complete processing, reduce costs, and conventionally can in rubber, add toughener.Therefore,, from rubber industryization application, people are devoted to rubber reinforcement mechanism and correlation technique research always.From zinc oxide to carbon black, then to the Application and Development of various packing strengthening agent and correlation technique, find emphasis and focus that efficient, easy, economic enhancement method and toughener are rubber scientific researches always.
White carbon black is a kind of very important white mineral filler, is widely used in the industrial circles such as plastics, rubber, coating and papermaking.But because the surface of white carbon black can be high, very easily assemble, in rubber, be difficult to disperse processing difficulties; Vulcanization accelerator is had to very strong adsorption, cause sulfuration delay and degree of crosslinking low, the problems such as difference of strengthening the property.So to use as toughener be that the organic modification surperficial with it is inseparable to white carbon black all the time.
At present, industrial multiplex stearic acid carries out surface modification to white carbon black, but is only physically modified, and the reactive force of silica particles and rubber matrix is very weak; Also useful coupling agent carries out modification to white carbon black, but cost is higher, preparation skill is complicated, be difficult to the shortcomings such as dispersed.In recent years, many investigators, in order to further expand and optimize the use properties of white carbon black filled composite materials, expand its Application Areas, and the research of functionalized polymer modified white carbon black also becomes a focus.[epoxy natural rubber grafting high-dispersion white carbon black strengthens preparation and the feature of native rubber composite material to Liu Jiwen, polymer journal, 2008,: 123-128] etc. (2) adopted the solid-state grafting white carbon black of epoxy natural rubber to prepare a kind of novel high-dispersion white carbon black, it is good dispersed and can obviously improve the reinforced effects to natural rubber that result has shown that grafting white carbon black has in natural rubber; Although the dispersiveness of white carbon black in rubber matrix obtained certain improvement, but still there is certain defect by solid-state grafting white carbon black, plasticate few, white carbon black disperses irregular, plasticate many, can interrupt rubber molecular chain, two aspects have all affected the performance of rubber composite, can not obtain desirable reinforcing effect.
Therefore, at present also need to provide a kind of dispersiveness of white carbon black in rubber matrix of can significantly improving can make again white carbon black can produce crosslinked with rubber molecular chain in rubber matrix, and can simplify the technical process of producing rubber item, be conducive to the automatization control of the course of processing, the preparation method of the high performance white carbon black/native rubber composite material of energy-conserving and environment-protective is that industry is expected.
Summary of the invention
The object of the invention is to solve through traditional modifier treatment white carbon black the problem to reinforcing rubber poor effect, strong by employing polarity, to contain active oh group hydroxyethyl methylacrylate rubber latex is to white carbon black graft modification, utilize consistency excellent between hydroxyethyl methylacrylate rubber latex and natural rubber latex, improve the dispersion effect of white carbon black in natural rubber latex, improve the strengthening action of white carbon black to natural rubber.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
Utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, comprise the steps:
In deionized water, add white carbon black and appropriate coupling agent and anion surfactant, stir ultrasonic dispersion, add subsequently appropriate emulsus hydroxyethyl methylacrylate rubber, continue to adopt and stir ultrasonic dispersion, prepare white carbon black emulsion dispersion body; Adopt appropriate nonionogenic tenside to stablize appropriate emulsus natural rubber simultaneously, then constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in emulsus natural rubber equably, under 50 ~ 70 ℃ of water bath condition, drip and cause linking agent simultaneously, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state; By this matrix material further by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of dry gluey state.
The deal of the emulsus natural rubber of described white carbon black, coupling agent, anion surfactant, weight by dry rubber emulsus hydroxyethyl methylacrylate rubber, nonionogenic tenside, weight by dry rubber, initiation linking agent (in weight part, lower same) is:
White carbon black: 10 ~ 80 parts; Coupling agent: 2 ~ 4 parts; Anion surfactant: 0.3 ~ 0.7 part; The emulsus hydroxyethyl methylacrylate rubber of weight by dry rubber: 5 ~ 40 parts; Nonionogenic tenside: 0.3 ~ 0.9 part; The emulsus natural rubber of weight by dry rubber: 100 parts; Cause linking agent: 1 ~ 3 part.
Utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, comprise the steps:
(1) preparation of modified white carbon black emulsion dispersion body:
In white carbon black, add ethanol, ultrasonic dispersion while stirring, then the anion surfactant that adds 2 ~ 4 parts of coupling agents through ethanol hydrolysis and 0.3 ~ 0.7 part, under 35 ℃ ~ 90 ℃ temperature condition, react 1 ~ 2 hour, and then add emulsus hydroxyethyl methylacrylate rubber, in temperature, be under 70 ℃ ~ 90 ℃ conditions, under ultrasonic dispersion while stirring simultaneously, react 1 ~ 2 hour, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black emulsion dispersion body;
(2) preparation of the white carbon black-native rubber composite material of latex state:
Adopt the concentrated natural latex that 0.3 ~ 0.9 portion of nonionogenic tenside is 60% to 100 parts of weight by dry rubber total solids levels to stablize, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, and then add initiation linking agent, in temperature, be under 70 ℃ ~ 90 ℃ conditions, stirring reaction 1 ~ 2 hour, obtains the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state;
(3) preparation of the white carbon black-native rubber composite material of dry gluey state:
By solidifying, compressing tablet, washing, dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-natural rubber compound of dry gluey state, adopt usual manner on rubber mixing machine, hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-natural rubber compound suitably to be plasticated, then add successively and cause linking agent, paraffinic based oil and rubber processing aids, mixing even, make white carbon black-native rubber composite material.
Utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, comprise the steps:
(1) preparation of modified white carbon black emulsion dispersion body:
In white carbon black, add ethanol, ultrasonic dispersion while stirring, then the anion surfactant that adds 2 ~ 4 parts of coupling agents through ethanol hydrolysis and 0.3 ~ 0.7 part, under 35 ℃ ~ 90 ℃ temperature condition, react 1 ~ 2 hour, and then add emulsus hydroxyethyl methylacrylate rubber, in temperature, be under 70 ℃ ~ 90 ℃ conditions, under ultrasonic dispersion while stirring simultaneously, react 1 ~ 2 hour, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black emulsion dispersion body;
(2) preparation of the white carbon black-native rubber composite material of dry gluey state:
By white carbon black emulsion dispersion body by solidifying, compressing tablet, washing, dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black of dry gluey state, then the natural rubber of the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black of dry gluey state and dry gluey state is adopted to the usual manner homogenize of plasticating on rubber mixing machine, after homogenize evenly, add successively and cause linking agent, paraffinic based oil and rubber processing aids, mixing even, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of doing gluey state.
Described white carbon black, is after just infiltrating by appropriate ethanol, to use the wet white carbon black of rinsed with deionized water, dioxide-containing silica 87%～95%, and particle diameter is 20～100 μ m.
Described coupling agent, optional sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester or three stearic acid isopropyl titanate titanic acid ester or sec.-propyl three oleic acid acyloxy titanic acid ester, preferably three stearic acid isopropyl titanate titanic acid ester.
Described anion surfactant, optional Sodium hexametaphosphate 99 or Sodium dodecylbenzene sulfonate or or potassium oleate, preferably Sodium dodecylbenzene sulfonate.
Described emulsus hydroxyethyl methylacrylate rubber, optional natural rubber is by the emulsus hydroxyethyl methylacrylate rubber of preparing with hydroxyethyl methylacrylate graft copolymerization, or by natural rubber latex by the hydroxyethyl methylacrylate latex prepared with hydroxyethyl methylacrylate graft copolymerization or be 5 ~ 50% by concentrated natural latex by preparing percentage of grafting with hydroxyethyl methylacrylate graft copolymerization, total solids level is 20 ~ 25% hydroxyethyl methylacrylate latex, the percentage of grafting that preferably concentrated natural latex is prepared by graft copolymerization is 5 ~ 50%, total solids level is 20 ~ 25% hydroxyethyl methylacrylate latex.
Described nonionogenic tenside, optional fatty alcohol-polyoxyethylene ether or sorbitol polyoxyethylene ether or polyoxyethylene nonylphenol ether, preferred fat polyoxyethylenated alcohol.
Described emulsus natural rubber, the natural rubber latex of optional Brazilian para ruber or concentrated natural latex or the concentrated natural latex that is 60% through centrifugal concentrating, total solids level, the concentrated natural latex that is preferably 60% through centrifugal concentrating, total solids level.
Described initiation linking agent, optional superoxide is as tertbutyl peroxide, ammonium persulphate or Potassium Persulphate, initiator system of ammonium persulfate.
Utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, comprise the steps:
Take 10 ~ 80 parts of white carbon blacks, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 2 ~ 4 part of three stearic acid isopropyl titanate titanic acid ester and 0.3 ~ 0.7 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 20 ~ 40 minutes, add subsequently that 5 ~ 40 parts of weight by dry rubber percentage of grafting are 5 ~ 50%, the hydroxyethyl methylacrylate rubber latex of total solids level 20 ~ 25%, continue to adopt and stir ultrasonic dispersion 20 ~ 40 minutes, prepare white carbon black emulsion dispersion body; Adopt the concentrated natural latex that 0.3 ~ 0.9 part of fatty alcohol-polyoxyethylene ether is 60% to 100 parts of weight by dry rubber total solids levels to stablize simultaneously, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, then drip 1 ~ 3 part of ammonium persulphate, after stirring, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state; By this matrix material further by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of dry gluey state.
The hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of described preparation can adopt conventional vulcanization system, as effective vulcanization system, semi effcient vulcanization system, peroxide vulcanizing system etc., make prevulcanized latex, by impregnation technology, produce various latex products; Also can adopt conventional machining technique to carry out mixing sulfuration, produce various dry glue goods.
The invention has the beneficial effects as follows:
(1) the hydroxyethyl methylacrylate rubber latex that employing is prepared by hydroxyethyl methylacrylate and natural rubber latex graft copolymerization is as the dispersion compatilizer between white carbon black and natural rubber latex, utilize consistency excellent between hydroxyethyl methylacrylate rubber latex and natural rubber and active hydroxyl, white carbon black bridging is received on the cross-linked network of rubber, improve significantly the dispersion effect of white carbon black in natural rubber, thereby realized the strong keying action between white carbon black and natural rubber, prepare high-performance white carbon black-native rubber composite material.
(2) tensile strength of the sulfide film of hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material that prepared by employing the present invention can reach 25 ~ 29MPa, and elongation rate of tensile failure can reach 700 ~ 950%, 300% stress at definite elongation can reach 3.5 ~ 7.0 MPa.
Embodiment
Below by example, the present invention is described in further details, these examples are only used for illustrating the present invention, do not limit the scope of the invention.
embodiment 1
Take the white carbon black that 10 parts of particle diameters are about 30 μ m, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 3 part of three stearic acid isopropyl titanate titanic acid ester and 0.3 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 30 minutes, add subsequently that 5 parts of weight by dry rubber percentage of grafting are 10%, the hydroxyethyl methylacrylate rubber latex of total solids level 20%, continue to adopt and stir ultrasonic dispersion 30 minutes, prepare white carbon black emulsion dispersion body, adopt the concentrated natural latex that 0.5 part of fatty alcohol-polyoxyethylene ether is 60% to 100 parts of weight by dry rubber total solids levels to stablize simultaneously, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, then drip 1.5 parts of ammonium persulphates, in temperature, be under 70 ℃ of conditions, stirring reaction 1 hour, obtain the hydroxyethyl methylacrylate grafting rubbers white carbon black-native rubber composite material of latex state, in this material, add 1.5 parts of Sulfurs, 0.6 part of zinc oxide, 0.6 part of zinc diethyldithiocarbamate (ZDC), 0.5 part of ethyl one phenyl zinc dithiocarbamate (PX), 0.5 part 2, 6-di-tert-butyl-4-methylphenol (anti-264), 60 ℃ of water-baths are vulcanized 1.5 hours, the tensile strength of the sulfuration glued membrane obtaining is 28.2MPa, elongation rate of tensile failure 920%, 300% stress at definite elongation 3.9 Mpa.
embodiment 2
Take the white carbon black that 80 parts of particle diameters are about 100 μ m, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 4 part of three stearic acid isopropyl titanate titanic acid ester and 0.7 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 30 minutes, add subsequently that 30 parts of weight by dry rubber grafting are 30%, the hydroxyethyl methylacrylate rubber latex of total solids level 25%, continue to adopt and stir ultrasonic dispersion 30 minutes, prepare white carbon black emulsion dispersion body; Adopt the concentrated natural latex that 0.9 part of fatty alcohol-polyoxyethylene ether is 60% to 100 parts of weight by dry rubber total solids levels to stablize simultaneously, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, after stirring, adopt that acetic acid solidifies, compressing tablet, washing, dry, make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black-natural rubber compound.On opening rubber mixing machine, in above-mentioned dry gluey matrix material, add successively subsequently 3.0 parts of ammonium persulphates, 3.5 parts of Sulfurs, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzothiazyl disulfides (altax), 0.7 part 2,6-di-tert-butyl-4-methylphenol (anti-264) mixingly vulcanizes 20 minutes after evenly at 160 ℃.The tensile strength of the sulfide film obtaining is 25.4MPa, elongation rate of tensile failure 710%, 300% stress at definite elongation 6.5MPa.
embodiment 3
Take the white carbon black that 40 parts of particle diameters are about 80 μ m, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 2 part of three stearic acid isopropyl titanate titanic acid ester and 0.3 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 30 minutes, add subsequently that 20 parts of weight by dry rubber percentage of grafting are 25%, the hydroxyethyl methylacrylate rubber latex of total solids level 20%, continue to adopt and stir ultrasonic dispersion after 30 minutes, adopt that ethanol solidifies, compressing tablet, washing, dry, make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black; Subsequently on opening rubber mixing machine by the natural rubber of 100 parts of dry shapes and above-mentionedly make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black and carry out blend, then add successively 2.0 parts of ammonium persulphates, 3.5 parts of Sulfurs, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzothiazyl disulfides (altax), 0.5 part 2,6-di-tert-butyl-4-methylphenol (anti-264) mixingly vulcanizes 20 minutes after evenly at 160 ℃.The tensile strength of the sulfide film obtaining is 26.9MPa, elongation rate of tensile failure 800%, 300% stress at definite elongation 5.8 MPa.
embodiment 4
Take the white carbon black that 50 parts of particle diameters are about 60 μ m, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 2 part of three stearic acid isopropyl titanate titanic acid ester and 0.3 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 30 minutes, add subsequently that 20 parts of weight by dry rubber percentage of grafting are 25%, the hydroxyethyl methylacrylate rubber latex of total solids level 20%, continue to adopt and stir ultrasonic dispersion after 30 minutes, adopt that ethanol solidifies, compressing tablet, washing, dry, make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black; Subsequently on opening rubber mixing machine by the natural rubber of 100 parts of dry shapes and above-mentionedly make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black and carry out blend, then add successively 2.0 parts of ammonium persulphates, 3.5 parts of Sulfurs, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzothiazyl disulfides (altax), 0.5 part 2,6-di-tert-butyl-4-methylphenol (anti-264) mixingly vulcanizes 20 minutes after evenly at 160 ℃.The tensile strength of the sulfide film obtaining is 26.3MPa, elongation rate of tensile failure 780%, 300% stress at definite elongation 5.5MPa.
embodiment 5
Take the white carbon black that 20 parts of particle diameters are about 100 μ m, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 4 part of three stearic acid isopropyl titanate titanic acid ester and 0.7 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 30 minutes, add subsequently that 30 parts of weight by dry rubber grafting are 30%, the hydroxyethyl methylacrylate rubber latex of total solids level 25%, continue to adopt and stir ultrasonic dispersion 30 minutes, prepare white carbon black emulsion dispersion body; Adopt the concentrated natural latex that 0.9 part of fatty alcohol-polyoxyethylene ether is 60% to 100 parts of weight by dry rubber total solids levels to stablize simultaneously, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, after stirring, adopt that acetic acid solidifies, compressing tablet, washing, dry, make dry gluey hydroxyethyl methylacrylate grafting rubbers white carbon black-natural rubber compound.On opening rubber mixing machine, in above-mentioned dry gluey matrix material, add successively subsequently 3.0 parts of ammonium persulphates, 3.5 parts of Sulfurs, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzothiazyl disulfides (altax), 0.7 part 2,6-di-tert-butyl-4-methylphenol (anti-264) mixingly vulcanizes 20 minutes after evenly at 160 ℃.The tensile strength of the sulfide film obtaining is 27.4MPa, elongation rate of tensile failure 810%, 300% stress at definite elongation 4.5MPa.
Claims (13)
1. utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, it is characterized in that: comprise the steps:
In deionized water, add white carbon black and appropriate coupling agent and anion surfactant, stir ultrasonic dispersion, add subsequently appropriate emulsus hydroxyethyl methylacrylate rubber, continue to adopt and stir ultrasonic dispersion, prepare white carbon black emulsion dispersion body; Adopt appropriate nonionogenic tenside to stablize appropriate emulsus natural rubber simultaneously, then constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in emulsus natural rubber equably, under 50 ~ 70 ℃ of water bath condition, drip and cause linking agent simultaneously, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state; By this matrix material further by solidifying, compressing tablet, washing, dry standard Chinese rubber conventional machining technique, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of dry gluey state.
2. the preparation method who utilizes hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material according to claim 1, is characterized in that: the emulsus natural rubber of described white carbon black, coupling agent, anion surfactant, weight by dry rubber emulsus hydroxyethyl methylacrylate rubber, nonionogenic tenside, weight by dry rubber, cause linking agent deal (take weight part) as:
White carbon black: 10 ~ 80 parts; Coupling agent: 2 ~ 4 parts; Anion surfactant: 0.3 ~ 0.7 part; The emulsus hydroxyethyl methylacrylate rubber of weight by dry rubber: 5 ~ 40 parts; Nonionogenic tenside: 0.3 ~ 0.9 part; The emulsus natural rubber of weight by dry rubber: 100 parts; Cause linking agent: 1 ~ 3 part.
3. utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, it is characterized in that: comprise the steps:
(1) preparation of modified white carbon black emulsion dispersion body:
In white carbon black, add ethanol, ultrasonic dispersion while stirring, then the anion surfactant that adds 2 ~ 4 parts of coupling agents through ethanol hydrolysis and 0.3 ~ 0.7 part, under 35 ℃ ~ 90 ℃ temperature condition, react 1 ~ 2 hour, and then add emulsus hydroxyethyl methylacrylate rubber, in temperature, be under 70 ℃ ~ 90 ℃ conditions, under ultrasonic dispersion while stirring simultaneously, react 1 ~ 2 hour, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black emulsion dispersion body;
(2) preparation of the white carbon black-native rubber composite material of latex state:
Adopt the concentrated natural latex that 0.3 ~ 0.9 portion of nonionogenic tenside is 60% to 100 parts of weight by dry rubber total solids levels to stablize, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, and then add initiation linking agent, in temperature, be under 70 ℃ ~ 90 ℃ conditions, stirring reaction 1 ~ 2 hour, has obtained the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state;
(3) preparation of the white carbon black-native rubber composite material of dry gluey state:
By solidifying, compressing tablet, washing, dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-natural rubber compound of dry gluey state, adopt usual manner on rubber mixing machine, hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-natural rubber compound suitably to be plasticated, then add successively and cause linking agent, paraffinic based oil and rubber processing aids, mixing even, make white carbon black-native rubber composite material.
4. utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen a preparation method for native rubber composite material, it is characterized in that: comprise the steps:
(1) preparation of modified white carbon black emulsion dispersion body:
In white carbon black, add ethanol, ultrasonic dispersion while stirring, then the anion surfactant that adds 2 ~ 4 parts of coupling agents through ethanol hydrolysis and 0.3 ~ 0.7 part, under 35 ℃ ~ 90 ℃ temperature condition, react 1 ~ 2 hour, and then add emulsus hydroxyethyl methylacrylate rubber, in temperature, be under 70 ℃ ~ 90 ℃ conditions, under ultrasonic dispersion while stirring simultaneously, react 1 ~ 2 hour, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black emulsion dispersion body;
(2) preparation of the white carbon black-native rubber composite material of dry gluey state:
By white carbon black emulsion dispersion body by solidifying, compressing tablet, washing, dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black of dry gluey state, then the natural rubber of the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black of dry gluey state and dry gluey state is adopted to the usual manner homogenize of plasticating on rubber mixing machine, after homogenize evenly, add successively and cause linking agent, paraffinic based oil and rubber processing aids, mixing even, make hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of doing gluey state.
5. according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, strengthen the preparation method of native rubber composite material, it is characterized in that: described white carbon black is after just infiltrating by appropriate ethanol, to use the wet white carbon black of rinsed with deionized water, dioxide-containing silica 87%～95%, particle diameter is 20～100 μ m.
6. according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, strengthen the preparation method of native rubber composite material, it is characterized in that: described coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester or three stearic acid isopropyl titanate titanic acid ester or sec.-propyl three oleic acid acyloxy titanic acid ester, preferably three stearic acid isopropyl titanate titanic acid ester.
7. according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, strengthen the preparation method of native rubber composite material, it is characterized in that: described anion surfactant is Sodium hexametaphosphate 99 or Sodium dodecylbenzene sulfonate or or potassium oleate, preferably Sodium dodecylbenzene sulfonate.
8. according to claim 1, the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in 3 or 4 strengthens the preparation method of native rubber composite material, it is characterized in that: described emulsus hydroxyethyl methylacrylate rubber is natural rubber by the emulsus hydroxyethyl methylacrylate rubber of preparing with hydroxyethyl methylacrylate graft copolymerization, or by natural rubber latex by the hydroxyethyl methylacrylate latex prepared with hydroxyethyl methylacrylate graft copolymerization or be 5 ~ 50% by concentrated natural latex by preparing percentage of grafting with hydroxyethyl methylacrylate graft copolymerization, total solids level is 20 ~ 25% hydroxyethyl methylacrylate latex, the percentage of grafting that preferably concentrated natural latex is prepared by graft copolymerization is 5 ~ 50%, total solids level is 20 ~ 25% hydroxyethyl methylacrylate latex.
9. according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, strengthen the preparation method of native rubber composite material, it is characterized in that: described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or sorbitol polyoxyethylene ether or polyoxyethylene nonylphenol ether, preferred fat polyoxyethylenated alcohol.
10. according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, strengthen the preparation method of native rubber composite material, it is characterized in that: the natural rubber latex that described emulsus natural rubber is Brazilian para ruber or concentrated natural latex or the concentrated natural latex that is 60% through centrifugal concentrating, total solids level, the concentrated natural latex that is preferably 60% through centrifugal concentrating, total solids level.
11. strengthen the preparation method of native rubber composite material according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3 or 4, it is characterized in that: described initiation linking agent is superoxide: tertbutyl peroxide, ammonium persulphate or Potassium Persulphate, initiator system of ammonium persulfate.
12. 1 kinds of preparation methods that utilize hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material, is characterized in that: comprise the steps:
Take 10 ~ 80 parts of white carbon blacks, add just and will after the ethanol of its infiltration, use rinsed with deionized water, add subsequently 2 ~ 4 part of three stearic acid isopropyl titanate titanic acid ester and 0.3 ~ 0.7 part of Sodium dodecylbenzene sulfonate and 100 parts of deionized waters, stir ultrasonic dispersion 20 ~ 40 minutes, add subsequently that 5 ~ 40 parts of weight by dry rubber percentage of grafting are 5 ~ 50%, the hydroxyethyl methylacrylate rubber latex of total solids level 20 ~ 25%, continue to adopt and stir ultrasonic dispersion 20 ~ 40 minutes, prepare white carbon black emulsion dispersion body; Adopt the concentrated natural latex that 0.3 ~ 0.9 part of fatty alcohol-polyoxyethylene ether is 60% to 100 parts of weight by dry rubber total solids levels to stablize simultaneously, constantly under agitation condition, above-mentioned white carbon black emulsion dispersion body is being mixed in stable concentrated natural latex equably, then drip 1 ~ 3 part of ammonium persulphate, after stirring, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of latex state; By this matrix material further by solidifying, compressing tablet, washing, the standard Chinese rubber conventional machining technique such as dry, obtain the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of dry gluey state.
13. strengthen the preparation method of native rubber composite material according to the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black that utilizes described in claim 1,3,4 or 12, it is characterized in that: the hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black-native rubber composite material of described preparation adopts conventional vulcanization system: efficient vulcanization system, semi effcient vulcanization system or peroxide vulcanizing system are made prevulcanized latex, by impregnation technology, produce various latex products; Or carry out mixing sulfuration by conventional machining technique, produce various dry glue goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518333.9A CN103554559B (en) | 2013-10-29 | 2013-10-29 | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310518333.9A CN103554559B (en) | 2013-10-29 | 2013-10-29 | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554559A true CN103554559A (en) | 2014-02-05 |
| CN103554559B CN103554559B (en) | 2015-10-14 |
Family
ID=50008934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310518333.9A Expired - Fee Related CN103554559B (en) | 2013-10-29 | 2013-10-29 | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554559B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131491A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Novel modified natural rubber composition |
| CN111548451A (en) * | 2020-06-18 | 2020-08-18 | 中国热带农业科学院农产品加工研究所 | High-performance rubber damping material and preparation method thereof |
| CN112480493A (en) * | 2019-09-12 | 2021-03-12 | 北京化工大学 | Rubber foaming material and preparation method thereof |
| CN114407266A (en) * | 2022-01-10 | 2022-04-29 | 青岛科技大学 | Preparation method of carbon black/natural latex composite material |
| CN114921008A (en) * | 2022-07-09 | 2022-08-19 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084258A (en) * | 2004-11-19 | 2007-12-05 | 株式会社普利司通 | Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire |
-
2013
- 2013-10-29 CN CN201310518333.9A patent/CN103554559B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084258A (en) * | 2004-11-19 | 2007-12-05 | 株式会社普利司通 | Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131491A (en) * | 2015-08-18 | 2015-12-09 | 合肥市再德高分子材料有限公司 | Novel modified natural rubber composition |
| CN105131491B (en) * | 2015-08-18 | 2018-03-02 | 合肥市再德高分子材料有限公司 | A kind of new modified natural rubber composition |
| CN112480493A (en) * | 2019-09-12 | 2021-03-12 | 北京化工大学 | Rubber foaming material and preparation method thereof |
| CN112480493B (en) * | 2019-09-12 | 2022-04-19 | 北京化工大学 | Rubber foaming material and preparation method thereof |
| CN111548451A (en) * | 2020-06-18 | 2020-08-18 | 中国热带农业科学院农产品加工研究所 | High-performance rubber damping material and preparation method thereof |
| CN114407266A (en) * | 2022-01-10 | 2022-04-29 | 青岛科技大学 | Preparation method of carbon black/natural latex composite material |
| CN114921008A (en) * | 2022-07-09 | 2022-08-19 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
| CN114921008B (en) * | 2022-07-09 | 2022-11-22 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554559B (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101418086B (en) | Method for preparing rice hull ash-natural rubber composite material | |
| CN103539976B (en) | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer nano-calcium carbonate to strengthen native rubber composite material | |
| CN103554559B (en) | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer white carbon black to strengthen native rubber composite material | |
| CN101456961B (en) | Method for preparing reactive nano calcium carbonate-native rubber composite material | |
| CN102838788B (en) | Shell powder-natural rubber composite material and preparation method thereof | |
| CN103554558B (en) | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer potter's clay to strengthen native rubber composite material | |
| CN103554560B (en) | A kind of preparation method of generated in-situ unsaturated fatty acid zinc salt reinforcement natural rubber | |
| CN105482480B (en) | A kind of bamboo fiber reinforcement thermoplastic | |
| CN104045868B (en) | A kind of preparation method of nano-cerium oxide/native rubber composite material | |
| CN104530613B (en) | Rubber-phase fluorinated polysiloxane thermoplastic elastomer with core-shell structure and preparation method of rubber-phase fluorinated polysiloxane thermoplastic elastomer | |
| CN102718995A (en) | Industrial lignin reinforcing rubber and preparation method of industrial lignin reinforcing rubber | |
| CN107474343B (en) | Method for preparing sea squirt nano microcrystalline cellulose/rubber nano composite material by one-pot method | |
| CN104072832B (en) | A kind of oil-filled oxygenation functionalized graphene emulsion beta-rubber and preparation method thereof altogether | |
| CN107418002A (en) | A kind of high-quality rubber seal | |
| CN102358799A (en) | Unsaturated polyester molding compound and preparation method thereof | |
| CN104312020A (en) | High-strength extension-resistant ageing-resistant modified butyl rubber material | |
| CN107501888B (en) | High-performance PC/ABS alloy material and preparation method thereof | |
| CN103665723A (en) | Method for preparing high-toughness high-strength polypropylene material through in-situ compatibilization | |
| CN102827406A (en) | Shell powder-epoxidized natural rubber composite material and preparation method thereof | |
| CN104497378A (en) | Anti-cracking high-performance rubber composite material and preparation method thereof | |
| CN104830081A (en) | Pulverization modified lignin, preparation method and applications thereof | |
| CN103102517B (en) | Preparation method of palm ash-natural rubber composite material | |
| CN103131068A (en) | Preparation method of reactive egg shell powder-epoxidized natural rubber composite material | |
| CN103113632A (en) | Method for preparing composite material of reaction type egg shell powder and natural rubber | |
| CN110734593A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151014 Termination date: 20181029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |