CN103570856A - Rubber and preparation method thereof - Google Patents
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Abstract
The invention discloses a rubber. The rubber is prepared from the following raw materials by weight: 60 to 70 parts of styrene, 40 to 50 parts of butadiene, 0.2 to 0.4 part of disodium ethylenediaminetetraacetate, 0.5 part of a molecular weight regulator, 0.04 part f an initiator, 5 to 10 parts of an emulsifier, 10 to 15 parts of a low temperature oil resistant monomer, 20 to 30 parts of a fire retardant, 5 to 10 parts of a lubricant, 0.5 to 0.8 part of a catalyst, 0.2 to 0.5 part of carbon black and 120 to 150 parts of deionized water. The rubber prepared in the invention has excellent performances; rigidity, hardness, wear resistance and the like of the rubber reach the standards of a product of a same kind in the world; since the low temperature oil resistant monomer and the fire retardant are added into the raw materials, the rubber has good cold resistance and flame resistance. A preparation method for the rubber has the advantages of easiness, easily controllable process, low energy consumption, short reaction time and substantial reduction in production cost.
Description
Technical field
The present invention relates to a kind of rubber and preparation method thereof.
Background technology
Rubber is divided into natural rubber and synthetic rubber.Natural rubber is mainly derived from para ruber, when the epidermis of this rubber tree is cut open, will flow out milky juice, is called latex, latex through cohesion, washing, moulding, be drying to obtain natural rubber.Synthetic rubber is made by artificial synthesis, adopts different raw material (monomer) can synthesize different types of rubber.Within 1900～1910 years, chemist C.D. Harris (Harris) structure of having measured natural rubber is the superpolymer of isoprene, and this is just for asynthetic rubber has opened up approach.Scholar SV NIKOLAY LEBEDEV (Lebedev Russianizes for 1910,1874-1934) take sodium Metal 99.5 makes 1 as initiator, 3-polymerizing butadiene becomes sodium butadiene rubber, has occurred successively again many new synthetic rubber kinds, as cis-1,4-polybutadiene rubber, chloroprene rubber, styrene-butadiene rubber(SBR) etc. later.Elastomeric output has substantially exceeded natural rubber, and wherein output maximum is styrene-butadiene rubber(SBR).
Rubber has the snappiness polymer materials of reversible deformation.At room temperature high resilience can produce compared with large deformation under very little External Force Acting, removes resilient after external force.Rubber belongs to complete amorphous polymer, and (T g) is low for its second-order transition temperature, and molecular weight is often very large, is greater than hundreds of thousands of.The molecular chain of rubber can be cross-linked, and when the rubber after being cross-linked is deformed by External Force Acting, has the ability of rapid recovery, and has good physical and mechanical property and chemical stability.Rubber is the basic raw material of rubber industry, is widely used in and manufactures tire, sebific duct, adhesive tape, cable and other various rubber items.
Rubber industry is one of important foundation industry of national economy, it not only provides daily life the indispensable light industry rubber product such as daily, medical for people, and provides various rubber production unit processed or rubber components to the heavy industry such as digging, traffic, building, machinery, electronics and new industry.Visible, the product category of rubber industry is various, and backward industry is very wide.At present, all there is diversified asynthetic rubber home and abroad, mainly contains: 1. chloroprene rubber, be called for short CR, and by chloroprene polymerization, made.There is good over-all properties, oil resistant, resistance to combustion, resistance to oxidation and resistance to ozone.But its density is larger, easily crystallization hardening under normal temperature, storage property is bad, and winter hardiness is poor.2. paracril, is called for short NBR, by divinyl and acrylonitrile compolymer, is made.Oil resistant, ageing-resistant performance are good, can in the air of 120 ℃ or in the oil of 150 ℃, use for a long time.In addition, also there is water tolerance, resistance to air loss and good adhesive property.3. silicon rubber, main chain is alternately comprised of silicone atom, on Siliciumatom with organic group.High-low temperature resistant, resistance to ozone, electrical insulating property is good.4. viton, contains the synthetic rubber of fluorine atom in molecular structure.Conventionally the fluorine atom number with fluorine-containing unit in multipolymer represents, as fluororubber 23, is that vinylidene fluoride is with the multipolymer of trifluorochloroethylene.Viton is high temperature resistant, oil resistant, resistance to chemical attack.5. thiorubber, is formed by the polysulfide polycondensation of saturated dihalide and basic metal or alkaline-earth metal.Have excellent oil resistant and solvent resistance, but intensity is not high, ageing resistance, processibility are bad, frowziness, many and paracril use.6. styrenerubber, by divinyl and styrene copolymerized making, the distinguishing feature of styrenerubber is that hardness own is high, intensity is good, and the physicals again with rubber, when share with various synthetic rubber or natural rubber, the performance such as rigidity, hardness, wear resistance, reduction shrinking percentage that can improve rubber item, can be widely used in shoemaking industry, tire industry, Printing industry and other industry, enjoys attention, but in prior art, prepare styrenerubber, cost is high, complex process, and energy consumption is high, product performance are poor, gradually can not satisfy the demands.In addition, also have urethanes, chlorohydrin rubber, acrylic elastomer etc.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of synthetic convenience, cost is low, energy consumption is low, the styrenerubber of excellent property, and its preparation method is provided.
The present invention is achieved by the following technical solutions:
, be to be made by the raw material of following weight part: 60～70 parts of vinylbenzene, 40～50 parts of divinyl, 0.2～0.4 part of disodium ethylene diamine tetraacetate, 0.5 part of molecular weight regulator, 0.04 part of initiator, 5～10 parts of emulsifying agents, 10～15 parts of low temperature oil resistant monomers, 20～30 parts of fire retardants, 5～10 parts of lubricants, 0.5～0.8 part of catalyzer, 0.2～0.5 part of carbon black, 120～150 parts of deionized waters.
Described molecular weight regulator is tert-dodecyl mercaptan.
Described initiator is ammonium persulphate or sodium bisulfite.
Described emulsifying agent is alkyl oxy diphenyl sulfide acid disodium.
Described low temperature oil resistant monomer is vinylformic acid ethoxy ethyl ester.
Described fire retardant is aluminium hydroxide or magnesium hydroxide or ammonium polyphosphate.
Described lubricant is silane auxiliary agent oil.
Described catalyzer is dibutyl tin laurate.
Preferably, be to be made by the raw material of following weight part: 65 parts of vinylbenzene, 45 parts of divinyl, 0.3 part of disodium ethylene diamine tetraacetate, 0.5 part of tert-dodecyl mercaptan, 0.04 part of ammonium persulphate, 8 parts of alkyl oxy diphenyl sulfide acid disodiums, 12 parts of vinylformic acid ethoxy ethyl esters, 25 parts, aluminium hydroxide, 8 parts of silane auxiliary agent oil, 0.6 part of dibutyl tin laurate, 0.4 part of carbon black, 140 parts of deionized waters.
The preparation method of described rubber is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, molecular weight regulator, emulsifying agent, lubricant, catalyzer and deionized water are mixed, after mixing, add initiator, at 40～70 ℃, react 30～40min, then add low temperature oil resistant monomer, fire retardant and carbon black, stir lower continuation and react 2～4 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The rubber that the present invention prepares, excellent property, its rigidity, hardness, wear resistance etc. all can reach international like product (HS-860) level, and, because having added low temperature oil resistant monomer, fire retardant in raw material, make it there is good winter hardiness, flame retardant resistance.Preparation method of the present invention is simple, and process is easily controlled, and energy consumption is low, and the reaction times is short, greatly reduces its production cost.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1 prepares styrenerubber
Formula is: 65 grams of vinylbenzene, 45 grams of divinyl, 0.3 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of ammonium persulphate, 8 grams of alkyl oxy diphenyl sulfide acid disodiums, 12 grams of vinylformic acid ethoxy ethyl esters, 25 grams, aluminium hydroxide, 8 grams of silane auxiliary agent oil, 0.6 gram of dibutyl tin laurate, 0.4 gram of carbon black, 140 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator ammonium persulfate, at 50 ℃, react 35min, then add vinylformic acid ethoxy ethyl ester, aluminium hydroxide and carbon black, stir lower continuation and react 3 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.5 ℃;
Mooney viscosity
(MV): 55;
Low temperature brittleness temperature :-39.7 ℃;
Hardness (Shao Er A): 86;
Tensile strength: 9.4MPa;
Tensile strength at yield: 24.3MPa;
Elongation at break (%): 367;
Permanent set (%): 6.
Embodiment 2 prepares styrenerubber
Formula is: 60 grams of vinylbenzene, 50 grams of divinyl, 0.2 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of sodium bisulfite, 10 grams of alkyl oxy diphenyl sulfide acid disodiums, 10 grams of vinylformic acid ethoxy ethyl esters, 30 grams of magnesium hydroxides, 5 grams of silane auxiliary agent oil, 0.8 gram of dibutyl tin laurate, 0.2 gram of carbon black, 120 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator sodium bisulfite, at 60 ℃, react 40min, then add vinylformic acid ethoxy ethyl ester, magnesium hydroxide and carbon black, stir lower continuation and react 4 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.3 ℃;
Mooney viscosity
(MV): 53;
Low temperature brittleness temperature :-39.5 ℃;
Hardness (Shao Er A): 85;
Tensile strength: 9.2MPa;
Tensile strength at yield: 23.9MPa;
Elongation at break (%): 362;
Permanent set (%): 6.
Embodiment 3 prepares styrenerubber
Formula is: 70 grams of vinylbenzene, 40 grams of divinyl, 0.4 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of ammonium persulphate, 5 grams of alkyl oxy diphenyl sulfide acid disodiums, 15 grams of vinylformic acid ethoxy ethyl esters, 20 grams of ammonium polyphosphates, 10 grams of silane auxiliary agent oil, 0.5 gram of dibutyl tin laurate, 0.5 gram of carbon black, 150 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator ammonium persulfate, at 70 ℃, react 30min, then add vinylformic acid ethoxy ethyl ester, ammonium polyphosphate and carbon black, stir lower continuation and react 3 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.2 ℃;
Mooney viscosity
(MV): 54;
Low temperature brittleness temperature :-39.3 ℃;
Hardness (Shao Er A): 84;
Tensile strength: 9.1MPa;
Tensile strength at yield: 23.5MPa;
Elongation at break (%): 359;
Permanent set (%): 6.
Embodiment 4 prepares styrenerubber
Formula is: 62 grams of vinylbenzene, 48 grams of divinyl, 0.3 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of ammonium persulphate, 6 grams of alkyl oxy diphenyl sulfide acid disodiums, 14 grams of vinylformic acid ethoxy ethyl esters, 23 grams, aluminium hydroxide, 9 grams of silane auxiliary agent oil, 0.6 gram of dibutyl tin laurate, 0.4 gram of carbon black, 130 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator ammonium persulfate, at 60 ℃, react 40min, then add vinylformic acid ethoxy ethyl ester, aluminium hydroxide and carbon black, stir lower continuation and react 2 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.4 ℃;
Mooney viscosity
(MV): 55;
Low temperature brittleness temperature :-39.6 ℃;
Hardness (Shao Er A): 86;
Tensile strength: 9.1MPa;
Tensile strength at yield: 24.2MPa;
Elongation at break (%): 365;
Permanent set (%): 6.
Embodiment 5 prepares styrenerubber
Formula is: 68 grams of vinylbenzene, 43 grams of divinyl, 0.4 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of sodium bisulfite, 6 grams of alkyl oxy diphenyl sulfide acid disodiums, 11 grams of vinylformic acid ethoxy ethyl esters, 28 grams of ammonium polyphosphates, 7 grams of silane auxiliary agent oil, 0.7 gram of dibutyl tin laurate, 0.3 gram of carbon black, 135 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator sodium bisulfite, at 55 ℃, react 40min, then add vinylformic acid ethoxy ethyl ester, ammonium polyphosphate and carbon black, stir lower continuation and react 3 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.5 ℃;
Mooney viscosity
(MV): 52;
Low temperature brittleness temperature :-39.8 ℃;
Hardness (Shao Er A): 86;
Tensile strength: 8.9MPa;
Tensile strength at yield: 23.8MPa;
Elongation at break (%): 363;
Permanent set (%): 6.
Embodiment 6 prepares styrenerubber
Formula is: 66 grams of vinylbenzene, 46 grams of divinyl, 0.3 gram of disodium ethylene diamine tetraacetate, 0.5 gram of tert-dodecyl mercaptan, 0.04 gram of ammonium persulphate, 7 grams of alkyl oxy diphenyl sulfide acid disodiums, 12 grams of vinylformic acid ethoxy ethyl esters, 26 grams of magnesium hydroxides, 7 grams of silane auxiliary agent oil, 0.7 gram of dibutyl tin laurate, 0.2 gram of carbon black, 145 grams of deionized waters.
Preparation method is: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, tert-dodecyl mercaptan, alkyl oxy diphenyl sulfide acid disodium, silane auxiliary agent oil, dibutyl tin laurate and deionized water are mixed, after mixing, add initiator ammonium persulfate, at 0 ℃, react 40min, then add vinylformic acid ethoxy ethyl ester, magnesium hydroxide and carbon black, stir lower continuation and react 3 hours, obtain rubber latex, after cohesion, being dried, obtain rubber.
The index determining of gained rubber is as follows:
Glass transition temperature Tg :-42.3 ℃;
Mooney viscosity
(MV): 54;
Low temperature brittleness temperature :-39.2 ℃;
Hardness (Shao Er A): 84;
Tensile strength: 9.1MPa;
Tensile strength at yield: 23.8MPa;
Elongation at break (%): 360;
Permanent set (%): 6.
Although the present invention has been made to further instruction above in conjunction with the embodiments; but be not construed as limiting the scope of the present invention; one of ordinary skill in the art should know; in the situation that not departing from design of the present invention, all different or improved technical scheme of having done is included in protection scope of the present invention.
Claims (9)
1. a rubber, is characterized in that: be to be made by the raw material of following weight part: 60～70 parts of vinylbenzene, 40～50 parts of divinyl, 0.2～0.4 part of disodium ethylene diamine tetraacetate, 0.5 part of molecular weight regulator, 0.04 part of initiator, 5～10 parts of emulsifying agents, 10～15 parts of low temperature oil resistant monomers, 20～30 parts of fire retardants, 5～10 parts of lubricants, 0.5～0.8 part of catalyzer, 0.2～0.5 part of carbon black, 120～150 parts of deionized waters.
2. rubber according to claim 1, is characterized in that: described molecular weight regulator is tert-dodecyl mercaptan.
3. rubber according to claim 1, is characterized in that: described initiator is ammonium persulphate or sodium bisulfite.
4. rubber according to claim 1, is characterized in that: described emulsifying agent is alkyl oxy diphenyl sulfide acid disodium.
5. rubber according to claim 1, is characterized in that: described low temperature oil resistant monomer is vinylformic acid ethoxy ethyl ester.
6. rubber according to claim 1, is characterized in that: described fire retardant is aluminium hydroxide or magnesium hydroxide or ammonium polyphosphate.
7. rubber according to claim 1, is characterized in that: described lubricant is silane auxiliary agent oil.
8. rubber according to claim 1, is characterized in that: described catalyzer is dibutyl tin laurate.
9. the preparation method of the rubber described in any one in claim 1～9, it is characterized in that: vinylbenzene, divinyl, disodium ethylene diamine tetraacetate, molecular weight regulator, emulsifying agent, lubricant, catalyzer and deionized water are mixed, after mixing, add initiator, at 40～70 ℃, react 30～40min, then add low temperature oil resistant monomer, fire retardant and carbon black, stir the lower reaction 2～4 hours that continues, obtain rubber latex, after cohesion, being dried, obtain rubber.
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| CN201210261186.7A CN103570856A (en) | 2012-07-26 | 2012-07-26 | Rubber and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080803A (en) * | 1997-11-19 | 2000-06-27 | Basf Aktiengesellschaft | Preparing coarse polymer dispersions |
| US20050288422A1 (en) * | 2003-11-19 | 2005-12-29 | John Burns | Rubber compositions of enhanced flame resistance, articles formed therefrom and related method |
| CN101125906A (en) * | 2006-08-17 | 2008-02-20 | 中国石油天然气集团公司 | Preparation method for small grainsize polybutadiene latex |
| CN101280075A (en) * | 2008-05-09 | 2008-10-08 | 西北师范大学 | Flame-retardant styrene-butadiene rubber |
| CN101649025A (en) * | 2009-06-06 | 2010-02-17 | 中国石油兰州石油化工公司 | Preparation method of carboxylic styrene butadiene latex |
-
2012
- 2012-07-26 CN CN201210261186.7A patent/CN103570856A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080803A (en) * | 1997-11-19 | 2000-06-27 | Basf Aktiengesellschaft | Preparing coarse polymer dispersions |
| US20050288422A1 (en) * | 2003-11-19 | 2005-12-29 | John Burns | Rubber compositions of enhanced flame resistance, articles formed therefrom and related method |
| CN101125906A (en) * | 2006-08-17 | 2008-02-20 | 中国石油天然气集团公司 | Preparation method for small grainsize polybutadiene latex |
| CN101280075A (en) * | 2008-05-09 | 2008-10-08 | 西北师范大学 | Flame-retardant styrene-butadiene rubber |
| CN101649025A (en) * | 2009-06-06 | 2010-02-17 | 中国石油兰州石油化工公司 | Preparation method of carboxylic styrene butadiene latex |
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Application publication date: 20140212 |