CN103159866A - Preparation method of reinforced powdered rubber - Google Patents
Preparation method of reinforced powdered rubber Download PDFInfo
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- CN103159866A CN103159866A CN2011104198592A CN201110419859A CN103159866A CN 103159866 A CN103159866 A CN 103159866A CN 2011104198592 A CN2011104198592 A CN 2011104198592A CN 201110419859 A CN201110419859 A CN 201110419859A CN 103159866 A CN103159866 A CN 103159866A
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Abstract
A preparation method of a reinforced rubber powder employs chemical reactions to bond organic siloxane to separant molecules, thus preparing a powdered rubber product with high tensile strength. The method comprises the specific steps of: adding 1-200 parts of organo-siloxane monomer containing unsaturated bonds, 1-35 parts of a molecular weight regulator and 0.1-0.5 part of an initiator into 100 weight parts of unsaturated fatty acid anhydride; conducting polymerization at 5-120 DEG C for 0.5-6.0 h; adding 80-120 parts of basic aqueous solution with mass concentration of 5%w-15%w into the generated mixture for saponification, thereby preparing a separant for standby; calculated by dry weight of the rubber, adding 1-50 parts of the reinforced separant obtained in the above step and 0-100 parts of a coagulant into 100 parts of latex; condensing the mixture into powder at -20-95 DEG C under stirring condition; and dehydrating to obtain the reinforced powdered rubber.
Description
Technical field
The present invention relates to a kind of preparation method of powdered rubber, specifically a kind of preparation method with powdered rubber of certain reinforcing function.
Background technology
The preparation method of powdered rubber mainly contains mechanical crushing method, spray-drying process and cohesion coating method etc.Three kinds of methods all need be used separant, and the separant effect is to prevent rubber particles surface adhesion, mainly divides inorganics and the large class of inorganics two, inorganics, as: calcium carbonate, talcum powder, carbon black, white carbon black, water glass etc.; Organism, as: macromolecule resin, divalence soap etc.
Carbon black in inorganic separant, white carbon black are widely used as the strengthening agent of rubber, and the former is very ripe, and the latter is popular research direction in recent years.The consistency of white carbon black and hydrocarbon rubbers is good not as carbon black, for improving the interface interaction between sizing material and filler, the various interfacial agents of normal employing, carry out modification as silane coupling agent, carbonates, polyvalent alcohol/amine etc., the white carbon black reinforcement vulcanizating glue physical performance of aforesaid method modification and dynamic properties all have improvement in various degree, still have gap and all are not suitable for the powdered rubber production field but compare with the black-reinforced effect.
White carbon black is directly used in the separant that powdered rubber is produced, what play due to it is only buffer action, not only do not promote the mechanical property of rubber, make it on the contrary variation, it is that properties-correcting agent prepares a kind of separant with reinforcing function that this patent adopts organo-siloxane, be used for the production of powdered rubber, made up the bad deficiency of consistency of white carbon black and hydrocarbon rubbers, utilize simultaneously this functionalization separant to realize powdered rubber mobility and high-intensity with showing property.
CN200410046023.2, the manufacture method of powdered rubber is that to adopt the stearates material be that the coacervation of separant becomes the powder technology.CN97110144.2, a kind of preparation method of high-molecular coating agent and application thereof are that the polymerisate under benzoyl peroxide causes makes through saponification by vinylbenzene and MALEIC ANHYDRIDE, can be used for preparing powdered rubber.Separant described in patent or coating only have antiseized effect, and rubber matrix is not had strengthening action.
Summary of the invention
The objective of the invention is to prepare a kind of separant that rubber is had reinforcing function, and use this separant to prepare the reinforced type powdered rubber.
The preparation method of reinforced type powdered rubber of the present invention comprises the steps: in the dried glue weight part of rubber, add 1～50 part of reinforced type separant in 100 parts of latex, add 0～100 part, flocculation agent, condensation powdering under-20 ℃～95 ℃ and agitation condition is through dehydrating to get reinforced type powdered rubber product;
The preparation method of described reinforced type separant is: take the unsaturated fatty acids acid anhydrides as 100 mass parts, add 1～200 part of the organo-siloxane monomer that contains unsaturated link(age) in 100 parts of unsaturated fatty acids acid anhydrides, fully mix, add 1～35 part of molecular weight regulator, add again 0.1～0.5 part of initiator, polymerase 10 .5～6.0h under 5～120 ℃ and agitation condition, the alkali aqueous solution that to add 80～120 parts of mass concentrations in the mixture that generates be 5%w～15%w makes its saponification, thereby makes separant.
Unsaturated fatty acids acid anhydrides of the present invention is the unsaturated fatty acids acid anhydrides that carbochain has 3～18 carbon atoms, specifically the different carbon chain lengths such as acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride, triolefin stearic acid acid anhydride and structure has the olefin(e) acid acid anhydride of saturation ratio scarcely, a preferred monoene stearic acid acid anhydride.
Its structural formula of organo-siloxane monomer that contains unsaturated link(age) is:
Wherein:
Y-contains the unsaturated aliphatic segment of 2～18 carbon, can be vinyl, propenyl, allyl group, sec.-propyl, pseudoallyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, ethynyl, 1-proyl, ethyl acetylene base, 1-pentynyl, 1-heptyne base, methacryloxypropyl, methacryloxy, preferred vinyl;
R
1, R
3-contain the alkoxyl group of 1～12 carbon, the aryloxy of 6～12 carbon, the siloxy of 3～12 carbon, can be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, hexyloxy, pentyloxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferred methoxyl group, oxyethyl group; R
1And R
3Be set as the purpose that contains alkoxyl group and be and add the effect of man-hour by heat and acid at powdered rubber and make the alkoxyl group hydrolysis, thus in rubbery system formation-O-Si-spacial framework, thereby base rubber is played strengthening action; If only have an alkoxyl group in the organo-siloxane monomer, only form dimer after its hydrolysis, can not form-the O-Si-spacial framework, do not have the effect of reinforcement.
R
2Can be and R
1Identical group can also be the saturated segment that contains 1～20 carbon, 1～8 cyclic alkane, aromatic hydrocarbon; Preferable methyl, ethyl, methoxyl group, oxyethyl group;
The organo-siloxane monomer that contains unsaturated link(age) of the present invention can be vinyltriethoxysilane, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two pentyloxys-hexyl silane, sec.-propyl two n-butoxy ethylsilane etc.
Molecular weight regulator of the present invention can be the molecular weight regulator of the Raolical polymerizable of all kinds such as DDM dodecyl mercaptan and derivative thereof, dialkyl dithio xanthate, tetraalkyl dithio xanthic amide, chloroform class material, dithio isocyanic ester.
Initiator of the present invention can be dibenzoyl peroxide (PhCO
2)
2, the peroxide initiators such as hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide can be also the azo-initiators such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl.
Alkali aqueous solution of the present invention can be water-soluble alkaline solutions such as NaOH, KOH, ammoniacal liquor.
Latex of the present invention can be the various latex such as styrene-butadiene latex, nitrile rubber, natural rubber latex, butadiene latex.
Flocculation agent of the present invention can be CaCl
2, MgSO
4, MgCl
2, Al
2SO
4, FeCl
3, CuCl
2, Ca (HSO
4)
2Deng soluble metal salt and composition thereof.
The know-why of foundation of the present invention is:
1, polyreaction
1. multipolymer
2. unsaturated acid anhydride autohemagglutination
3. unsaturated siloxane autohemagglutination
2, saponification reaction
1. with the resultant of sodium hydroxide with the multipolymer saponification
2. the saponification of unsaturated acid anhydride autopolymer
3, hydrolysis reaction
n(H
3CO-)
3Si-R
The hydrolysis such as (hot, sour condition){ R-Si (O-)
3-
n-H
3n+ 3n CH
3OH
As shown in above-mentioned chemical equation, in the present invention, the unsaturated fatty acids acid anhydrides issues living Raolical polymerizable with the organo-siloxane initiator effect that contains unsaturated link(age), make the generation low-molecular weight copolymer by adding molecular weight regulator and controlling transformation efficiency, carry out after saponification reaction product stand-by; When above-mentioned separant was used for the coacervation powdered rubber and prepares, hydrophobic end and the rubber particles of low molecule multipolymer were affine, and its water-wet side is wrapped in the rubber particles surface uniformly, and water-wet side is at Ca
2+Become the hydrophobic side under effect, thereby the rubber latex breakdown of emulsion forms the powdered rubber particle.
This powdered rubber particle makes the hydrolysis of reinforcement group form (spacial framework Si-O-Si-) by heating or acidic conditions in the processed and applied process, being wound around each other of the structure of (-Si-O-Si-) and rubber molecule formed spacial framework, mechanical property that can Reinforced Rubber matrix, thus rubber matrix is played the effect of reinforcement.
The present invention is bonded to organo-siloxane on the separant molecule by chemical reaction, add at powdered rubber and make the organo-siloxane hydrolysis by heat and sour effect man-hour, thereby formation-O-Si-spacial framework in rubbery system, thereby base rubber is played strengthening action.For example, enhancement type powder styrene butadiene rubber of the present invention is compared with the common designations powder styrene butadiene rubber, and tensile strength can improve the 20%w left and right.
Description of drawings
Fig. 1 is reinforced type powdered rubber structural representation;
Fig. 2 is the space structure schematic diagram that forms in the reinforced type powdered rubber.
Embodiment
It is as described below that the present invention specifically implements required material auxiliary agent:
(1) contain the organo-siloxane monomer of unsaturated link(age): vinyltriethoxysilane, vinyl diethyl one Ethoxysilane, vinyl trimethoxy siloxanes, SILVER REAGENT, the Shanghai general siloxanes of remittance company limited;
(2) unsaturated fatty acids acid anhydrides: monoene stearic acid acid anhydride, monoene caproic anhydride, diene stearic acid acid anhydride, triolefin stearic acid acid anhydride etc., SILVER REAGENT, the Jiangsu people contain trade limited liability company;
(3) initiator: dibenzoyl peroxide (PhCO
2)
2, Diisopropyl azodicarboxylate, molecular weight regulator: DDM dodecyl mercaptan, conditioning agent fourth, Lanzhou Petrochemical auspicious prosperous company;
(4) latex: styrene-butadiene latex, nitrile rubber are poly-, butadiene latex, and Lanzhou Petrochemical rubber plant produces; Natural rubber latex: treasured island, Hainan board natural rubber latex commodity.
%w representation quality concentration in the present invention.
Embodiment 1:
The preparation of step 1. reinforced type separant: add 30 parts of vinyltriethoxysilane monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 12 parts of mercaptan, then add 0.11 part of (PhCO
2)
2, carry out polyreaction 2.1h under 75 ℃ and agitation condition, add the NaOH solution of the 6%w of 100 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 9 parts of reinforced type separants in step 1 in the 100 mass parts styrene-butadiene latexes, add CaCl
233 parts, flocculation agent carries out condensation powdering under 45 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butylbenzene rubber tensile strength (18.7MPa), the enhancement type powder butylbenzene rubber tensile strength 22.4MPa of embodiment 1 has improved 19.7%.
Comparative Examples 1:
The preparation of step 1. separant: add vinyl diethyl-30 parts of Ethoxysilane monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 12 parts of mercaptan, then add 0.11 part of (PhCO
2)
2, carry out polyreaction 2.1h under 75 ℃ and agitation condition, add the NaOH solution of the 6%w of 100 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. powdered rubber: add 9 parts of separants in step 1 in the 100 mass parts styrene-butadiene latexes, add CaCl
233 parts, flocculation agent carries out condensation powdering under 45 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (18.7MPa), the powder butadiene-styrene rubber tensile strength 18.8MPa of Comparative Examples 1 does not obviously improve.
Embodiment 2:
The preparation of step 1. separant: add 17 parts of vinyl triethoxyl siloxanyl monomers in 100 mass parts monoene caproic anhydrides, fully mix, add 9 parts of mercaptan, then add 0.50 part of (PhCO
2)
2, carry out polyreaction 1.05h under 98 ℃ and agitation condition, add the KOH solution of the 15%w of 120 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 1 part of reinforced type separant in step 1 in the 100 mass parts styrene-butadiene latexes, add MgSO
438 parts, flocculation agent carries out condensation powdering under-20 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.9MPa), the reinforced type powder butadiene-styrene rubber tensile strength 21.1MPa of embodiment 2 has improved 17.8%.
Comparative Examples 2:
The preparation of step 1. separant: add the KOH solution of the 15%w of 120 parts to make its saponification in 100 mass parts monoene caproic anhydrides, thereby it is stand-by to make separant;
The preparation of step 2. powdered rubber: add 1 part of separant in step 1 in the 100 mass parts styrene-butadiene latexes, add MgSO
438 parts, flocculation agent carries out condensation powdering under-20 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.9MPa), the powder butadiene-styrene rubber tensile strength 17.1MPa of Comparative Examples 2, intensity slightly reduces.
Embodiment 3:
The preparation of step 1. separant: add vinyl two pentyloxys-200 parts of hexyl silane monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 5 parts of mercaptan, add again 0.50 part of hydrogen phosphide cumene, carry out polyreaction 3h under 8 ℃ and agitation condition, add the NH of the 5%w of 80 parts in the mixture that generates
4OH solution makes its saponification, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 50 parts of reinforced type separants in step 1 in the 100 mass parts styrene-butadiene latexes, add 0 part, flocculation agent, carry out condensation powdering under 95 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.5MPa), the enhancement type powder butadiene-styrene rubber tensile strength 20.9MPa of embodiment 3 has improved 19.4%w.
Comparative Examples 3:
The preparation of step 1. separant: commercially available separant sodium stearate;
The preparation of step 2. powdered rubber: add 50 parts of commercially available separant sodium stearate in 100 mass parts styrene-butadiene latexes, add 0 part, flocculation agent, carry out condensation powdering under 95 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.2MPa), the powder butadiene-styrene rubber tensile strength 17.5MPa of Comparative Examples 3 does not significantly improve.
Embodiment 4:
The preparation of step 1. separant: add 100 parts of vinyl triethoxyl siloxanyl monomers in 100 mass parts diene stearic acid acid anhydrides, fully mix, add 15 parts of dialkyl dithio xanthates, then add 0.40 part of (PhCO
2)
2, carry out polyreaction 6.0h under 120 ℃ and agitation condition, add the NaOH solution of the 11%w of 100 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 20 parts of separants in step 1 in the 100 mass parts styrene-butadiene latexes, add FeCl
325 parts, flocculation agent carries out condensation powdering under 25 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (18.2MPa), the enhancement type powder butadiene-styrene rubber tensile strength 21.6MPa of embodiment 4 has improved 18.7%.
Comparative Examples 4:
The preparation of step 1. separant: add 100 parts of vinyl triethoxyl siloxanyl monomers in 100 mass parts diene stearic acid acid anhydrides, fully mix, add the NaOH solution of the 11%w of 100 parts to make its saponification in mixture, thereby it is stand-by to make separant;
The preparation of step 2. powdered rubber: add 20 parts of separants in step 1 in the 100 mass parts styrene-butadiene latexes, add FeCl
325 parts, flocculation agent carries out condensation powdering under 25 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (18.2MPa), the powder butadiene-styrene rubber tensile strength 18.0MPa of Comparative Examples 4, intensity does not improve.
Embodiment 5:
The preparation of step 1. separant: add 150 parts of sec.-propyl two n-butoxy ethylsilane monomers in 100 mass parts triolefin stearic acid acid anhydrides, fully mix, add 12 parts of mercaptan, then add 0.25 part of (PhCO
2)
2, carry out polyreaction 0.5h under 10 ℃ and agitation condition, add the KOH solution of the 13%w of 120 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 30 parts of reinforced type separants in step 1 in the 100 mass parts styrene-butadiene latexes, add CuCl
230 parts, flocculation agent carries out condensation powdering under 60 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.5MPa), the enhancement type powder butadiene-styrene rubber tensile strength 22.4MPa of embodiment 5 has improved 28.0%.
Comparative Examples 5:
The preparation of step 1. separant: add the KOH solution of the 13%w of 120 parts to make its saponification in 100 mass parts triolefin stearic acid acid anhydrides, thereby it is stand-by to make separant;
The preparation of step 2. powdered rubber: add 30 parts of separants in step 1 in the 100 mass parts styrene-butadiene latexes, add CuCl
230 parts, flocculation agent carries out condensation powdering under 60 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
Direct 150 parts of blending sec.-propyl two n-butoxy ethylsilane monomers in the powdered rubber product, sample preparation.After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.5MPa), the tensile strength 17.1MPa of Comparative Examples 5, intensity does not improve.
Embodiment 6:
The preparation of step 1. separant: add 80 parts of vinyl triethoxyl siloxanyl monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 14 parts of mercaptan, add again 0.35 part of Diisopropyl azodicarboxylate, carry out polyreaction 2.2h under 55 ℃ and agitation condition, add the NaOH solution of the 6%w of 80 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 40 parts of separants in step 1 in the 100 mass parts styrene-butadiene latexes, add MgCl
22 parts, flocculation agent carries out condensation powdering under 70 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.6MPa), the enhancement type powder butadiene-styrene rubber tensile strength 21.2MPa of embodiment 6 has improved 20.4%.
Comparative Examples 6:
The preparation of step 1. separant: commercially available separant potassium oleate;
The preparation of step 2. powdered rubber: add 40 parts of commercially available separant potassium oleates in 100 mass parts styrene-butadiene latexes, add MgCl
22 parts, flocculation agent carries out condensation powdering under 70 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
Direct 80 parts of blending vinyltriethoxysilane monomers in the powdered rubber.After tested, compare with ordinary powder butadiene-styrene rubber tensile strength (17.6MPa), the powder butadiene-styrene rubber tensile strength 17.3MPa of Comparative Examples 6, intensity does not improve.
Embodiment 7:
The preparation of step 1. separant: add vinyl diethoxy-30 parts of ethylsilane monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 11 parts of mercaptan, then add 0.19 part of (PhCO
2)
2, carry out polyreaction 2.3h under 86 ℃ and agitation condition, add the NaOH solution of the 7%w of 80 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 5.9 parts of reinforced type separants in step 1 in the 100 mass parts nitrile rubberes, add CaCl
229 parts, flocculation agent carries out condensation powdering under 80 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder butadiene-acrylonitrile rubber tensile strength (20.6MPa), the enhancement type powdered nitrile rubber glue tensile strength 25.1MPa of embodiment 7 has improved 22.0%.
Comparative Examples 7:
The preparation of step 1. separant: add the NaOH solution of the 7%w of 80 parts to make its saponification in 100 mass parts monoene stearic acid acid anhydrides, thereby it is stand-by to make separant;
The preparation of step 2. powdered rubber: add 5.9 parts of reinforced type separants in step 1 in the 100 mass parts nitrile rubberes, add CaCl
229 parts, flocculation agent carries out condensation powdering under 80 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
Direct 30 parts of blending vinyl diethoxy one ethylsilane monomers in the powdered rubber, sample preparation.After tested, compare with ordinary powder butadiene-acrylonitrile rubber tensile strength (20.6MPa), the powdered nitrile rubber glue tensile strength 20.9MPa of Comparative Examples 7 does not significantly improve.
Embodiment 8:
The preparation of step 1. separant: add 105 parts of vinyltrimethoxy silane monomers in 100 mass parts monoene stearic acid acid anhydrides, fully mix, add 9.4 parts of mercaptan, then add 0.39 part of (PhCO
2)
2, carry out polyreaction 1.3h under 77 ℃ and agitation condition, add the NaOH solution of the 8%w of 109 parts to make its saponification in the mixture that generates, thereby it is stand-by to make separant;
The preparation of step 2. reinforced type powdered rubber: add 17 parts of reinforced type separants in step 1 in the 100 mass parts butadiene latexes, add Ca (HSO
4)
233 parts, flocculation agent carries out condensation powdering under 15 ℃ of temperature and agitation condition, through dehydrating to get reinforced type powdered rubber product.
After tested, compare with ordinary powder divinyl glue tensile strength (21.6MPa), the enhancement type powder divinyl glue tensile strength 26.13MPa of embodiment 8 has improved 21.9%.
Comparative Examples 8:
The preparation of step 1. separant: commercially available separant potassium rosinate;
The preparation of step 2. powdered rubber: add 17 parts of commercially available separant potassium rosinates in 100 mass parts butadiene latexes, add Ca (HSO
4)
233 parts, flocculation agent carries out condensation powdering under 15 ℃ of temperature and agitation condition, through dehydrating to get the powdered rubber product.
Direct 105 parts of blending vinyltrimethoxy silane monomers in the powdered rubber, sample preparation.After tested, compare with ordinary powder divinyl glue tensile strength (21.6MPa), the enhancement type powder divinyl glue tensile strength 19.3MPa of embodiment 8 slightly reduces.
Claims (9)
1. the preparation method of a reinforced type powdered rubber, is characterized in that comprising the steps:
In the dried glue weight part of rubber, add 1～50 part of reinforced type separant in 100 parts of latex, add 0～100 part, flocculation agent, condensation powdering under-20 ℃～95 ℃ and agitation condition is through dehydrating to get reinforced type powdered rubber product;
The preparation method of described reinforced type separant is: take the unsaturated fatty acids acid anhydrides as 100 mass parts, add 1～200 part of the organo-siloxane monomer that contains unsaturated link(age) in 100 parts of unsaturated fatty acids acid anhydrides, fully mix, add 1～35 part of molecular weight regulator, add again 0.1～0.5 part of initiator, polymerase 10 .5～6.0h under 5～120 ℃ and agitation condition, the alkali aqueous solution that to add 80～120 parts of mass concentrations in the mixture that generates be 5%w～15%w makes its saponification, thereby makes separant.
2. preparation method as claimed in claim 1, is characterized in that described unsaturated fatty acids acid anhydrides is the unsaturated fatty acids acid anhydrides that carbochain has 3～18 carbon atoms.
3. preparation method as claimed in claim 1, is characterized in that described unsaturated fatty acids acid anhydrides is selected from acrylic anhydride, iso-butylene acid anhydrides, monoene caproic anhydride, monoene lauric anhydride, monoene stearic acid acid anhydride, diene stearic acid acid anhydride, triolefin stearic acid acid anhydride.
4. preparation method as claimed in claim 1, is characterized in that it is vinyltriethoxysilane, vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, vinyl two pentyloxys-hexyl silane, sec.-propyl two n-butoxy ethylsilane that the described organo-siloxane monomer that contains unsaturated link(age) is selected from.
5. preparation method as claimed in claim 1, is characterized in that described molecular weight regulator is DDM dodecyl mercaptan, dialkyl dithio xanthate, tetraalkyl dithio xanthic amide, chloroform class material, dithio isocyanic ester.
6. preparation method as claimed in claim 1, it is characterized in that described initiator is dibenzoyl peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyclohexyl formonitrile HCN, azo-bis-iso-dimethyl.
7. preparation method as claimed in claim 1, is characterized in that described alkali aqueous solution is NaOH, KOH, ammonia soln.
8. the method for claim 1, is characterized in that described latex is styrene-butadiene latex, nitrile rubber, natural rubber latex, butadiene latex.
9. the method for claim 1, is characterized in that described flocculation agent is CaCl
2, MgSO
4, Mg Cl
2, Al
2SO
4, FeCl
3, CuCl
2, Ca (HSO
4)
2
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Cited By (2)
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|---|---|---|---|---|
| CN105732690A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Rubber reinforcing agent, preparation method thereof, and preparation method of butadiene styrene rubber |
| WO2020087952A1 (en) * | 2018-10-29 | 2020-05-07 | 青岛科技大学 | Method for flocculating fresh latex |
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| JPS5938206A (en) * | 1982-08-30 | 1984-03-02 | Toyo Soda Mfg Co Ltd | Prevention of coagulation of powdered rubber |
| CN1175603A (en) * | 1997-05-24 | 1998-03-11 | 华南理工大学 | Method for preparing high-molecular coating agent and use thereof |
| CN1673262A (en) * | 2004-03-24 | 2005-09-28 | 中国石油天然气股份有限公司 | Powdered high styrene rubber and its prepn process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732690A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Rubber reinforcing agent, preparation method thereof, and preparation method of butadiene styrene rubber |
| WO2020087952A1 (en) * | 2018-10-29 | 2020-05-07 | 青岛科技大学 | Method for flocculating fresh latex |
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| CN103159866B (en) | 2014-11-26 |
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