CN109627502A - A kind of methyl methacrylate rubber and native rubber composite material and preparation method thereof - Google Patents
A kind of methyl methacrylate rubber and native rubber composite material and preparation method thereof Download PDFInfo
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- CN109627502A CN109627502A CN201811337752.1A CN201811337752A CN109627502A CN 109627502 A CN109627502 A CN 109627502A CN 201811337752 A CN201811337752 A CN 201811337752A CN 109627502 A CN109627502 A CN 109627502A
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
Abstract
The present invention relates to native rubber composite material technical fields, more particularly to a kind of methyl methacrylate rubber and native rubber composite material and preparation method thereof, the preparation method includes the following steps: that (1) first weighs Heveatex, it is diluted with water, it stirs evenly, surfactant is added while stirring, adds tetren, is configured to latex mixed liquor.(2) methyl methacrylate monomer is added.(3) by latex mixed liquor heating water bath to 40-60 DEG C, initiator is added dropwise, isothermal reaction 3-7h obtains methyl methacrylate rubber lotion；Heveatex is added in methyl methacrylate rubber lotion, then heating or acid coagulation, methyl methacrylate rubber/natural rubber mixed rubber is made；(4), above-mentioned mixed rubber, natural rubber, silica, the mixing of other auxiliary agents of carbon black machine are weighed, is vulcanized using mechanical dry method blending technology, methyl methacrylate rubber and native rubber composite material is made.Composite material produced by the present invention has good processing performance and mechanical property.
Description
Technical field
The present invention relates to native rubber composite material technical fields, and in particular to a kind of methyl methacrylate rubber and natural rubber are compound
Material and preparation method thereof.
Background technique
Natural rubber (NR) due to wider molecular weight distribution, good processing performance and excellent mechanical performance,
It is widely used in tire tread glue, especially engineering tire field.Rubber product must pass through the efficient reinforcement side of filler
It can use.Since 20th century, carbon black (CB) is always the most important reinforcing agent of rubber product, the 90- of whole world CB consumption
95% is used for rubber industry, and tire is even more to have accounted for 67.5%.But with increasingly prominent, the carbon black price of the energy and environmental crisis
High, the high environmental pollution of process bring, so that exploitation non-carbon black filler, especially can form nano composite structure with rubber
Inorganic filler, instead of or part replace carbon black, become an important development direction of current rubber science and industry.
Wherein, SiO2It is an important replacement of carbon black, is widely used in rubber product.Because of SiO2Improving rubber
While glue processing performance, rubber fissipation factor (tan δ) can also be increased to the dependence of temperature, heat is reduced and roll resistance
Power, the wear-resisting and wet-sliding resistant performance for improving sizing material also become the one of current rubber industry with " green tire " that this is extended out
A key areas.
Polymolecularity SiO2Tire can be made to obtain better comprehensive performance (low viscosity, low-rolling-resistance and high wet-sliding resistant, resistance to
Mill property), but SiO2Surface can be bigger, easy to reunite in rubber matrix, leads to that sizing material wearability is poor, hysteresis loss is big.Therefore
Improve SiO2Dispersibility of the particle in NR is the key that the exploitation of high-performance NR masterbatch.Surface modification is to obtain polymolecularity
White carbon black important channel, coupling agent are to improve SiO2The main modifying agent of dispersibility.It is added in silica compound silane coupled
Agent can make tire three norms reach optimum balance.In addition, in addition to SiO2Outside own face property, the property of rubber matrix
The dispersion of white carbon black is had an important influence, shows that the polar group of nonpolar rubber matrix grafting can be with the pole of filler
Property group generate strong effect.In NR system, most typically epoxy natural rubber (ENR) improves SiO2Divide in NR
Scattered example, compared to NR, ENR strand has epoxy group, and polarity increases, and interacts with filler grain stronger.But this side
The research in face is not also that very system, Compatibilization Mechanism of the ENR as expanding material require further study.In addition, ENR price is high
It is expensive, cause production cost to rise, also inhibits its application in tire industry.
For methyl methacrylate rubber for epoxy natural rubber, cost has preferable application prospect the bottom of compared with.With polar monomer
The natural rubber of methyl methacrylate-grafted modified non-polar, prepared methyl methacrylate rubber and natural rubber can be with arbitrary proportions
Miscible, resulting mixed rubber can improve highly polar silica and nonpolar natural rubber as Interfacial compatibilization agent
Between compatibility, enhance interface binding power between the two, formed between silica and natural rubber strand and mutually seeped
Thoroughly, the network structure combine closely, being intertwined has important researching value.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of methyl methacrylate rubber and
The preparation method of native rubber composite material, the preparation method pass through the side that is copolymerized with polar monomer methyl methacrylate-grafted
Method introduces polarity group in natural rubber strand, prepares methyl methacrylate rubber；Further according to similar compatibility principle, with methyl methacrylate rubber
For expanding material, improve the compatibility between nonpolar natural rubber and polar filler silica；Then pass through enhancing rubber
Binding force between matrix and filler promotes the dispersibility of filler in the base, and then improves the mechanical property of composite material.
Another object of the present invention is to provide a kind of methyl methacrylate rubber and native rubber composite material, which has
Good processing performance and mechanical property, stretch Ying Li ﹑ tensile strength surely and tearing strength is much better than silica/carbon black filling
Natural gum, reinforcing property and wear-resisting property and silica/carbon black filling glue are suitable, and heat and rolling resistance significantly lower than white carbon black/
Carbon black filled glue.
The purpose of the invention is achieved by the following technical solution: a kind of preparation of methyl methacrylate rubber and native rubber composite material
Method includes the following steps:
(1) Heveatex for first weighing 100 parts by weight, being diluted with water mass concentration is 20%-45%, is stirred evenly,
The surfactant of 0.01-10 parts by weight is added while stirring, adds the tetren of 0.03-5.0 parts by weight, is configured to
Latex mixed liquor；
(2) methyl methacrylate monomer for weighing 30-50 parts by weight is added in above-mentioned latex mixed liquor, stirring point
It dissipates；
(3) 0.03- is added dropwise to 40-60 DEG C in the latex mixed liquor heating water bath after addition methyl methacrylate monomer
The initiator of 5.0 parts by weight, isothermal reaction 3-7h obtain methyl methacrylate rubber lotion；100 parts by weight are added in methyl methacrylate rubber lotion
Heveatex, be diluted with water into mass concentration be 20%-45% lotion, then heating or acid coagulation, through overcuring, squeeze
Pressure, granulation, washing and dry, obtained methyl methacrylate rubber/natural rubber mixed rubber；
(4), the above-mentioned mixed rubber of 5-70 parts by weight, the natural rubber of 30-95 parts by weight, 10-50 parts by weight are weighed
Silica, the silane coupling agent of the Tan Hei ﹑ 0.1-5.0 parts by weight of 10-50 parts by weight, 0.1-10 parts by weight anti-aging agent,
The sulphur of 0.1-10 parts by weight, the promotor of 0.1-5 parts by weight, the zinc oxide of 0.1-15 parts by weight and 0.1-10 parts by weight it is hard
Resin acid mixing, is vulcanized using mechanical dry method blending technology, and methyl methacrylate rubber and native rubber composite material is made.
Preferably, the Heveatex is that Heveatex, concentrated natural latex, the centrifugal concentrating of Brazilian para ruber are total
Solid content is the concentrated natural latex of 55%-65%.
Preferably, the surfactant is lauryl sodium sulfate or oleic acid amine.
Preferably, the initiator is cumyl hydroperoxide or tert-butyl hydroperoxide.
Preferably, the silica is nano silica.
Preferably, the nano silica is fumed nano silica, precipitation method nano silica, colloidal sol coagulate
Glue method nano silica.
Preferably, the silane coupling agent is double-(γ-triethoxy silicon substrate propyl) tetrasulfide.
Preferably, the anti-aging agent is N- phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-to benzene
Diamines, N-N'- diphenyl-p-phenylenediamine and 4, at least one of 4' a pair of (2,2- dimethyl benzyl) diphenylamines.
Preferably, the promotor is N tert butyl benzothiazole 2 sulfenamide.
A kind of methyl methacrylate rubber and native rubber composite material, the composite material include following component by weight:
The beneficial effects of the present invention are: preparation method of the invention by with polar monomer methyl methacrylate-grafted
The method of copolymerization introduces polarity group in natural rubber strand, prepares methyl methacrylate rubber；Further according to similar compatibility principle, with
Methyl methacrylate rubber is expanding material, improves the compatibility between nonpolar natural rubber and polar filler silica；Then pass through
Enhance the binding force between rubber matrix and filler, promotes the dispersibility of filler in the base, and then improve the power of composite material
Learn performance.
Composite material of the invention substitutes part natural rubber by using methyl methacrylate rubber, is used as natural rubber/titanium dioxide
Silicon/carbon black interface adhesive, compatilizer and toughener, while also can be used as the reinforcing agent of natural rubber, prepared is novel
Composite material determines to stretch that Ying Li ﹑ La stretches Qiang Du ﹑ tearing strength and ageing-resistant performance is superior to white carbon black comparative sample, compares with carbon black
Sample performance is suitable, and heat and rolling resistance are significantly lower than carbon black comparative sample.The modified existing hard charcoal of advanced composite material (ACM) of methyl methacrylate rubber
The advantages of black comparative sample low-heat-generation and low rolling hinder, and have the good mechanical property of carbon black comparative sample concurrently.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method of methyl methacrylate rubber and native rubber composite material, includes the following steps: that (1) first weighs 100 weights
The Heveatex for measuring part, being diluted with water mass concentration is 20%, stirs evenly, the oleic acid of 0.4 parts by weight is added while stirring
Amine adds the tetren of 0.2 parts by weight, is configured to latex mixed liquor.
(2) methyl methacrylate monomer for weighing 30 parts by weight is added in above-mentioned latex mixed liquor, is dispersed with stirring.
(3) 0.5 weight will be added dropwise when the latex mixed liquor heating water bath after methyl methacrylate monomer is added to 50 DEG C
The tert-butyl hydroperoxide of part, 60 DEG C of isothermal reaction 6h of water-bath obtain methyl methacrylate rubber lotion；It is added in methyl methacrylate rubber lotion
The Heveatex of 100 parts by weight is diluted with water into the lotion that mass concentration is 20%, then heating or acid coagulation, through overdone
Change, squeeze, being granulated, washing and is dry, methyl methacrylate rubber/natural rubber mixed rubber is made；
(4), weigh the above-mentioned mixed rubber of 10 parts by weight, the natural rubber of 90 parts by weight, 50 parts by weight silica,
Double-[γ-(triethoxysilicane) propyl] tetrasulfide, the anti-aging agent of 1 parts by weight, 1.5 of 4 parts by weight of Tan Hei ﹑ of 50 parts by weight
The sulphur of parts by weight, the N tert butyl benzothiazole 2 sulfenamide of 1 parts by weight, the zinc oxide of 1.5 parts by weight and 1 parts by weight
Stearic acid, vulcanized using mechanical dry method blending technology, methyl methacrylate rubber and native rubber composite material be made；
The silica is fumed nano silica；
The Heveatex is the concentrated natural latex that centrifugal concentrating total solid content is 60%；
The anti-aging agent is N- phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-p-phenylenediamine, N-
N'- diphenyl-p-phenylenediamine or 4,4' a pair of (2,2- dimethyl benzyl) diphenylamines.
Embodiment 2
The method of specific preparation method and embodiment 1 is essentially identical, and different places are: keeping latex quality concentration
It is 30%.
Embodiment 3
The method of specific preparation method and embodiment 2 is essentially identical, and different places are；Keep latex quality concentration
It is 40%.
Embodiment 4
The method of specific preparation method and embodiment 1 is essentially identical, and different places are: one is to maintain reaction temperature
40 DEG C, two be to maintain latex quality concentration be 40%.
Embodiment 5
The method of specific preparation method and embodiment 1 is essentially identical, and different places are: methyl methacrylate
Dosage is 50 parts.
Embodiment 6-9
The method of specific preparation method and embodiment 1 is essentially identical, and different places are: methyl methacrylate rubber and natural rubber
The deal ratio of glue is respectively as follows: 10/90,15/85,20/80 and 30/70.
The performance test of methyl methacrylate rubber made from embodiment 9 and native rubber composite material is as shown in the table:
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. the preparation method of a kind of methyl methacrylate rubber and native rubber composite material, characterized by the following steps:
(1) Heveatex for first weighing 100 parts by weight, being diluted with water mass concentration is 20%-45%, is stirred evenly, while stirring
The surfactant that 0.01-10 parts by weight are added in side is mixed, the tetren of 0.03-5.0 parts by weight is added, is configured to latex
Mixed liquor；
(2) methyl methacrylate monomer for weighing 30-50 parts by weight is added in above-mentioned latex mixed liquor, is dispersed with stirring；
(3) by the latex mixed liquor heating water bath after addition methyl methacrylate monomer to 40-60 DEG C, 0.03-5.0 weight is added dropwise
The initiator of part is measured, isothermal reaction 3-7h obtains methyl methacrylate rubber lotion；The day of 100 parts by weight is added in methyl methacrylate rubber lotion
Right latex, be diluted with water into mass concentration be 20%-45% lotion, then heating or acid coagulation, through overcuring, extruding,
Granulation, washing and dry, obtained methyl methacrylate rubber/natural rubber mixed rubber；
(4), weigh the above-mentioned mixed rubber of 5-70 parts by weight, the natural rubber of 30-95 parts by weight, 10-50 parts by weight dioxy
SiClx, the silane coupling agent of the Tan Hei ﹑ 0.1-5.0 parts by weight of 10-50 parts by weight, 0.1-10 parts by weight anti-aging agent, 0.1-10
The stearic acid-mixed of the sulphur of parts by weight, the promotor of 0.1-5 parts by weight, the zinc oxide of 0.1-15 parts by weight and 0.1-10 parts by weight
It closes, is vulcanized using mechanical dry method blending technology, methyl methacrylate rubber and native rubber composite material is made.
2. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the natural gum
Cream is the concentration day that Heveatex, concentrated natural latex, the centrifugal concentrating total solid content of Brazilian para ruber are 55%-65%
Right latex.
3. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the surface is living
Property agent be lauryl sodium sulfate or oleic acid amine.
4. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the initiator
For cumyl hydroperoxide or tert-butyl hydroperoxide.
5. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the titanium dioxide
Silicon is nano silica.
6. a kind of methyl methacrylate rubber according to claim 5 and native rubber composite material, it is characterised in that: the nanometer two
Silica is fumed nano silica, precipitation method nano silica, sol-gal process nano silica.
7. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the silane is even
Joining agent is double-(γ-triethoxy silicon substrate propyl) tetrasulfide.
8. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the anti-aging agent
For N- phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-p-phenylenediamine, N-N'- diphenyl-p-phenylenediamine
At least one of with 4,4' a pair of (2,2- dimethyl benzyl) diphenylamines.
9. a kind of methyl methacrylate rubber according to claim 1 and native rubber composite material, it is characterised in that: the promotor
For N tert butyl benzothiazole 2 sulfenamide.
10. a kind of methyl methacrylate rubber and native rubber composite material, it is characterised in that: the composite material include by weight with
Lower component:
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811337752.1A CN109627502B (en) | 2018-11-12 | 2018-11-12 | Composite material of natural rubber and preparation method thereof |
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| CN201811337752.1A CN109627502B (en) | 2018-11-12 | 2018-11-12 | Composite material of natural rubber and preparation method thereof |
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| CN109627502B CN109627502B (en) | 2021-03-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736400A (en) * | 2021-09-29 | 2021-12-03 | 福建友谊胶粘带集团有限公司 | Glue for bright blue protective film and bright blue protective film |
| CN115232373A (en) * | 2022-08-02 | 2022-10-25 | 泉州匹克鞋业有限公司 | Light rubber sole material and preparation method thereof |
| CN116515178A (en) * | 2023-06-07 | 2023-08-01 | 中国热带农业科学院农产品加工研究所 | Ageing-resistant heavenly stems and earthly branches rubber and natural rubber composite material and preparation method thereof |
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| JP2001302965A (en) * | 2000-04-21 | 2001-10-31 | Toyo Chem Co Ltd | Undercoating and adhesive tape |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736400A (en) * | 2021-09-29 | 2021-12-03 | 福建友谊胶粘带集团有限公司 | Glue for bright blue protective film and bright blue protective film |
| CN115232373A (en) * | 2022-08-02 | 2022-10-25 | 泉州匹克鞋业有限公司 | Light rubber sole material and preparation method thereof |
| CN115232373B (en) * | 2022-08-02 | 2023-08-22 | 泉州匹克鞋业有限公司 | Light rubber sole material and preparation method thereof |
| CN116515178A (en) * | 2023-06-07 | 2023-08-01 | 中国热带农业科学院农产品加工研究所 | Ageing-resistant heavenly stems and earthly branches rubber and natural rubber composite material and preparation method thereof |
| CN116515178B (en) * | 2023-06-07 | 2023-10-20 | 中国热带农业科学院农产品加工研究所 | Ageing-resistant heavenly stems and earthly branches rubber and natural rubber composite material and preparation method thereof |
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