CN103539949B - A kind of preparation method of high-performance liquid styrene butadiene rubber - Google Patents
A kind of preparation method of high-performance liquid styrene butadiene rubber Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of high-performance liquid styrene butadiene rubber, comprise the following steps: in reaction flask, add ethanol, add terpine resin after being heated to 80 ~ 110 DEG C, be stirred to and dissolve completely, add the thickening material of dissolving, be uniformly mixed.Water, styrene-butadiene latex, emulsifying agent, molecular weight regulator is added successively in polymeric kettle, after nitrogen replacement, add modified terpene resin, stirring heating, still temperature to be polymerized adds initiator when reaching 30 ~ 60 DEG C, under 30 ~ 60 DEG C of polymerization temperatures, reacts 5 ~ 8 hours, add terminator, obtained graft latex.Get graft latex and add condensing field, add water, anti-aging agent, trialkyl ammonia chloride, stirring heating, under 20 ~ 80 DEG C of condensation temperatures, add flocculation agent, at 20 ~ 80 DEG C, stirring is carried out slaking for 1 ~ 3 hour, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.The feature that obtained high-performance liquid styrene butadiene rubber has: combined styrene content 23.5 ~ 26.5, number-average molecular weight
Description
Technical field
The present invention relates to the preparation method of coating fluid rubber, particularly relate to a kind of preparation method of high-performance liquid styrene butadiene rubber.
Background technology
Fluid rubber is an important kind of rubber, and number-average molecular weight is between 500 ~ 10000.It is reported, the throughput of the various fluid rubber in the whole world reaches 200kt/a.Fluid rubber is of a great variety, and liquid acrylonitrile butadiene rubber, liquid styrene butadiene rubber and liquid isoprene rubber are all important kinds of fluid rubber, have outstanding application advantage in respective field.
Liquid styrene butadiene rubber is divinyl and cinnamic low-molecular weight copolymer, and emulsion polymerization liquid styrene-butadiene rubber(SBR) Industrial products have appearred for 1962 in molecular weight 2000 ~ 15000 the earliest.Liquid styrene butadiene rubber has excellent electrical insulation capability and physicals, and is insoluble to common organic solvents, heats not melting.The feature of liquid styrene butadiene rubber is good with the intermiscibility of some conventional rubber, and therefore they can use in blending, also can simultaneously absorb fillers and oil product.Because these blending ingredients are uniformly dispersed, cast good fluidity, therefore injection moldable produces vulcanite goods, also can be used as the softening agent of styrene-butadiene rubber(SBR), paracril and chloroprene rubber, or as sizing agent, sealing material etc.Terpine resin has that look shallow, high rigidity, high adhesive force, solvability are good, oxidation-resistance and Heat stability is good, good consistency is had with polymkeric substance, during for the agent of SBR adhesion rubber, force of cohesion and good tack, especially excellent property in quick adhesion can be maintained.Terpine resin is grafted to liquid styrene butadiene rubber when being used for coating, drastically increases adhesive performance.
CN200510032745.7 high strong adhesive, this tackiness agent comprises chloroprene rubber, grafted monomer, thickening material, dispersion agent, tackifier, catalyzer, oxidation inhibitor, solvent, filler etc.The method thickening material adds in chloroprene rubber mixing process, adds grafted monomer, dispersion agent, catalyzer etc. in dissolution process, then through again mixing and make high strong adhesive.In the method, thickening material can be carboxymethyl cellulose, and grafted monomer is ester class.CN200310112091.X polyvinyl chloride film adhesive, this tackiness agent is combined by a certain percentage by tackifying resin, VAE emulsion, emulsifying agent, softening agent, thickening material, organic solvent and water.The step of this invention is mixed with organic solvent by tackifying resin and dissolves; Emulsifying agent and softening agent are joined in the tackifying resin solution of the first step gained, is uniformly mixed; Emulsifying agent is sim alkylphenol polyoxyethyl ether, dodecyl phenenyl sulfate, and softening agent is dibutyl phthalate ester class.After thickening material and water mixed dissolution, join in second step gained mixture with the speed of 10 ~ 200ml/min under the agitation condition of 1200 ~ 4000r/min, first form w/o type emulsion, anti-phasely obtain O/W type emulsion afterwards; 3rd step gained mixture is joined in VAE emulsion, is uniformly mixed, can product be obtained.The high hold tack glue of CN200910195111.1 mono-kind, is made up of natural rubber, oil rubber SIS, naphthenic oil, petroleum resin, natural terpene resins, rubber accelerator and oxidation inhibitor.Described in CN201010225123.7, CN201010502113.3, the raw material of coating comprises: terpolymer EP rubber, teflon resin, SBR, terpine resin, SBS, anti-old dispersing auxiliary etc.CN201010106727.X solvent-free polyurethane adhesive for flexible package, at least formed by A, B two kinds of component mixtures, component A is the base polyurethane prepolymer for use as containing terminal isocyanate group end-blocking, and B component is the composite composition of the butylbenzene fluid rubber containing terminal hydroxy group and/or the polyester polyol of butyronitrile fluid rubber containing end carboxyl and polyether glycol.CN201010105813.9 primer coating for extrusion complex of soft package is the mono-component polyurethane polymkeric substance be polymerized by the polyester polyol containing liquid end hydroxy styrene-butadiene rubber and polyisocyanate solution.In the present invention, make consisting of of the raw material weight percentage of effective constituent: containing the polyester polyol 35%-50% of liquid end hydroxy styrene-butadiene rubber, polyisocyanates 10%-25%, ethyl acetate 30%-50%.CN200410062252.3 waterproof paint, is made up of terpolymer EP rubber, styrene-butadiene rubber(SBR), solidifying agent, tenderizer, promotor, vulcanizing agent, antiager and filler.What CN02125508.3, CN02125504.0, CN02125507.5 introduced is the synthetic method of liquid end hydroxy styrene-butadiene rubber, and with divinyl, vinylbenzene for monomer, organo-peroxide is initiator, organic ketone, C
1-C
6organic Alcohol is solvent, the free radical polymerisation process carried out, and it is characterized in that employing reaction suppressor before the reaction, while using reaction suppressor before the reaction, also can use terminator after the reaction.
US4448956A describes polyamide grafts low-molecular-weight liquid paracril etc.JP57042720A describes as obtaining a kind of epoxy resin, is realized liquid acrylonitrile butadiene rubber modification by a kind of triphenylphosphine catalysis.The foreign patents such as JP57149324A, JP57021427A, JP56106918A report the utilization of fluid rubber.
Both domestic and external be reported as fluid rubber the utilization of different field or by fluid rubber to various polymer modification, and mostly be liquid acrylonitrile butadiene rubber, liquid isoprene rubber etc.; Or by end group to liquid rubber modified.The present invention utilizes common liquid styrene butadiene rubber emulsion polymerisation process, and to liquid styrene butadiene rubber modification, method is simple, reliable.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-performance liquid styrene butadiene rubber, adopt direct coacervation to prepare a kind of high-performance liquid styrene butadiene rubber.
A kind of preparation method of high-performance liquid styrene butadiene rubber is:
In reaction flask, add ethanol, after being heated to 80 ~ 110 DEG C, add terpine resin, be stirred to it and dissolve completely, add the ether of cellulose of dissolving, be uniformly mixed, obtained modified terpene resin.Water, styrene-butadiene latex, emulsifying agent, molecular weight regulator is added successively in polymeric kettle, after nitrogen replacement, add modified terpene resin, stirring heating, still temperature to be polymerized adds initiator when reaching 30 ~ 60 DEG C, under 30 ~ 60 DEG C of polymerization temperatures, reacts 5 ~ 8 hours, add terminator, obtained graft latex.Get graft latex and add condensing field, 1 adds water, anti-aging agent, trialkyl ammonia chloride, stirring heating, under 20 ~ 80 DEG C of condensation temperatures, add flocculation agent, at 20 ~ 80 DEG C, stirring is carried out slaking for 1 ~ 3 hour, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.
In the present invention, the properties-correcting agent of terpine resin is ether of cellulose, as sodium carboxymethylcellulose pyce, Vltra tears sodium, Xylo-Mucine, sodium hydroxyethyl cellulose, and preferably carboxymethyl cellulose sodium.
Present invention also offers the best preparation method of described a kind of high-performance liquid styrene butadiene rubber, be specially:
1) modification of terpine resin: in reaction flask, adding 100 parts of mass percent concentrations is the ethanol of 75%, is heated to 80 ~ 110 DEG C, add 0.1 ~ 0.6 part of terpine resin, startup agitator is stirred to it and dissolves completely, then adds 0.1 ~ 0.5 part of ether of cellulose dissolved, is uniformly mixed.
2) preparation of graft latex: add 50 ~ 150 parts, water, styrene-butadiene latex 100 parts, 2 ~ 10 parts of emulsifying agents, 5 ~ 15 parts of molecular weight regulators in polymeric kettle successively, after nitrogen replacement, add 5 ~ 15 parts of modified terpene resins, stir, heat, when still temperature to be polymerized reaches 30 ~ 60 DEG C, add 0.1 ~ 0.4 part of initiator, stir 0.8 ~ 1h, then under 30 ~ 60 DEG C of polymerization temperatures, react 5 ~ 8 hours, add 0.1 ~ 0.5 part of terminator, obtained graft latex.
3) condense: get 100 parts of graft latexes and add condensing field, add 20 ~ 100 parts of water, 0.2 ~ 0.5 part of anti-aging agent, stirring heating, under 20 ~ 80 DEG C of condensation temperatures, add 3 ~ 15 parts of flocculation agent, at 20 ~ 80 DEG C, stirring is carried out slaking for 1 ~ 3 hour, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.
In the present invention, ether of cellulose is before adding terpine resin, preferably dissolves in water, and the mass ratio of the consumption of water and the add-on of ether of cellulose is 100 ︰ (0.1 ~ 0.8).Preferably 100 ︰ (0.1 ~ 0.3), for making it dissolve faster, need to be heated to 50 ~ 80 DEG C, preferably 70 ~ 80 DEG C.
The dissolving of terpine resin in the present invention, comparatively fast dissolves for making terpine resin and need be heated to 80 ~ 110 DEG C, preferably 90 ~ 100 DEG C.
In the present invention, in 100 parts of ethanol, the add-on of terpine resin is 0.1 ~ 0.6 part, preferably 0.2 ~ 0.4 part.
In the present invention terpine resin modification procedure in, the consumption of ether of cellulose is 0.1 ~ 0.5 part, preferably 0.1 ~ 0.3 part.
In the preparation process of graft latex of the present invention, described emulsifying agent is Sulfates, Sulfonates, and in order to ensure the stability of latex system and obtain higher percentage of grafting, preferred disproportionated rosin soap, consumption is 2 ~ 10 parts, preferably 4 ~ 6 parts.
In the preparation process of graft latex of the present invention, the molecular weight regulator used is selected from tert-dodecyl mercaptan, uncle ten carbon mercaptan, uncle 14 carbon mercaptan, uncle 16 carbon mercaptan, preferred tertiary DDM dodecyl mercaptan, and consumption is 5 ~ 15 parts, preferably 7 ~ 12 parts.
In the preparation process of graft latex of the present invention, the add-on of modified terpene resin is 5 ~ 15 parts, preferably 5 ~ 10 parts.
In the preparation process of graft latex of the present invention, described initiator adopts diazoamino compound or persulphate, preferred diazoamino compound, and as diazoamino acid sodium, consumption is 0.2 ~ 1.0 part, preferably 0.2 ~ 0.4 part.
In the present invention, the terminator adopted is selected from Sodium dimethyldithiocarbamate 40min, quinhydrones, and consumption is 0.2 ~ 1.0 part, preferably 0.2 ~ 0.4 part.
In the preparation process of graft latex of the present invention, polymerization temperature is 30 ~ 60 DEG C, preferably 40 ~ 50 DEG C, reacts 5 ~ 8 hours.
The anti-aging agent adopted in the present invention is N-Octyl-N '-phenyl-ρ-Ursol D, styrenated phenol etc., optimization styrene phenol.Aging inhibitor dosage is 0.2 ~ 0.8 part, preferably 0.3 ~ 0.5 part.
In the present invention, emulsion condensation temperature is 20 ~ 80 DEG C, preferably 20 ~ 30 DEG C.
The flocculation agent adopted is polymer coagulant, sulfuric acid etc.Described polymer coagulant is selected from acrylamide and styrene sulfonate, ligninsulfonate, vinylformic acid, methacrylic acid etc., as Sodium styrene sulfonate, styrene sulfonic acid calcium etc.
Flocculation agent consumption is 3 ~ 15 parts, preferably 5 ~ 10 parts.
Be 20 ~ 80 DEG C at curing temperature after graft latex of the present invention cohesion, preferably 60 ~ 80 DEG C.Time is 1 ~ 3 hour, preferably 2 ~ 3 hours.High-performance liquid styrene butadiene rubber performance prepared by the inventive method: combined styrene content 23.5 ~ 26.5, number-average molecular weight
viscosity 30 ~ 50(25 DEG C) PaS, functionality is close to 2.
Relative to the preparation of current liquid styrene butadiene rubber, method of modifying, advantage of the present invention has:
(1) terpine resin is applied in styrene-butadiene rubber(SBR) sizing agent, has and maintains force of cohesion and good tack, especially more excellent in quick adhesion.And styrene-butadiene latex and terpine resin grafting are as coating, coating high molecular crosslink density can be improved, the compactness of coating, snappiness and the sticking power to base material can be increased again.
(2) ether of cellulose mechanism of modification is that hydrophobic main chain and surrounding water molecules are by hydrogen bond association, improve the fluid volume of polymkeric substance itself, decreases the space of Particle free activity, thus improves system viscosity.
(3) ether of cellulose modified terpene resin, both interact, and the webbed chelation structure of shape, makes the performance of terpine resin modification butadiene-styrene rubber better.
(4) ether of cellulose modified terpene resin reinforcement liquid styrene butadiene rubber is used for doing coating, and the adhesive property of the coating both enhanced can reduce costs again.
(5) relative to the modification of current liquid styrene butadiene rubber end group, this method of modifying is not only simple to operate, and reliably, and cost is low.
(6) liquid styrene butadiene rubber is mainly used to do softening agent, sizing agent and sealing material etc. at present, and liquid styrene butadiene rubber of the present invention can be used to do high-grade paint, expands its range of application.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but and the scope of unrestricted the claims in the present invention protection.
Raw material sources:
Divinyl (B), vinylbenzene (S): CNPC's Lanzhou Petrochemical is produced; Sodium carboxymethylcellulose pyce, Xylo-Mucine: commercially available industrial goods; Terpine resin: commercially available prod; Other auxiliary agent provides by CNPC's Lanzhou Petrochemical.
Embodiment 1
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 50 DEG C, adds 0.1 part of sodium carboxymethylcellulose pyce, and startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 80 DEG C, add 0.1 part of terpine resin, be stirred to it and dissolve completely, then add 0.1 part of sodium carboxymethylcellulose pyce dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 50 parts, water, styrene-butadiene latex 100 parts, 4 parts of disproportionated rosin soaps, 5 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 15 parts of modified terpene resins, stir, heat, add 0.3 part of diazoamino acid sodium when still temperature to be polymerized reaches 30 DEG C, stir 1h, then under 30 DEG C of polymerization temperatures, react 8 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 100 parts, 0.5 part of styrenated phenol, 0.02 part of trialkyl ammonia chloride, stirring heating, under 80 DEG C of condensation temperatures, add 15 parts of sulfuric acid, at 80 DEG C, stirring is carried out slaking for 3 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 35(25 DEG C) PaS, functionality is close to 2.
Comparative example 1
Then styrene-butadiene latex grafting terpine resin, with embodiment 1, just not to terpine resin modification, namely directly to condense, experimental result: combined styrene content 23.5, number-average molecular weight by experiment condition
viscosity 26(25 DEG C) PaS, functionality is close to 2.
Embodiment 2
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 80 DEG C, adds 0.6 part of sodium carboxymethylcellulose pyce, and startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.It is 100 parts in the quality of ethanol, in another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 110 DEG C, add 0.6 part of terpine resin, be stirred to it and dissolve completely, then add 0.2 part of sodium carboxymethylcellulose pyce dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 150 parts, water, styrene-butadiene latex 100 parts, 10 parts of disproportionated rosin soaps, 10 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 5 parts of modified terpene resins, stir, heat, add 0.4 part of diazoamino acid sodium when still temperature to be polymerized reaches 60 DEG C, stir 1h, then under 60 DEG C of polymerization temperatures, react 5 hours, add 0.5 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 100 parts, 0.5 part of styrenated phenol, 0.08 part of trialkyl ammonia chloride, stirring heating, under 30 DEG C of condensation temperatures, add 15 parts of sulfuric acid, at 30 DEG C, stirring is carried out slaking for 3 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 50(25 DEG C) PaS, functionality is close to 2.
Comparative example 2
Then styrene-butadiene latex grafting terpine resin, with embodiment 2, just not to terpine resin modification, namely directly to condense, experimental result: combined styrene content 23.5, number-average molecular weight by experiment condition
viscosity 23(25 DEG C) PaS, functionality is close to 2.
Embodiment 3
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 60 DEG C, adds 0.3 part of Xylo-Mucine, and startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 90 DEG C, add 0.5 part of terpine resin, be stirred to it and dissolve completely, then add 0.3 part of Xylo-Mucine dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 100 parts, water, styrene-butadiene latex 100 parts, 6 parts of disproportionated rosin soaps, 15 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 10 parts of modified terpene resins, stir, heat, add 0.3 part of diazoamino acid sodium when still temperature to be polymerized reaches 40 DEG C, stir 0.8h, then under 40 DEG C of polymerization temperatures, react 8 hours, add 0.2 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 50 parts, 0.3 part of styrenated phenol, 0.05 part of trialkyl ammonia chloride, stirring heating, under 50 DEG C of condensation temperatures, add 12 parts of sulfuric acid, at 50 DEG C, stirring is carried out slaking for 2 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 24.5, number-average molecular weight
viscosity 45(25 DEG C) PaS, functionality is close to 2.
Comparative example 3
Experiment condition, with embodiment 3, just not to latex grafting, namely directly adds terpine resin is modified in agglomeration process.Experimental result: combined styrene content 24.0, number-average molecular weight
viscosity 20(25 DEG C) PaS, functionality is close to 2.
Embodiment 4
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 70 DEG C, adds 0.4 part of Xylo-Mucine, and startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 100 DEG C, add 0.3 part of terpine resin, be stirred to it and dissolve completely, then add 0.4 part of Xylo-Mucine dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 70 parts, water, styrene-butadiene latex 100 parts, 8 parts of disproportionated rosin soaps, 8 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 7 parts of modified terpene resins, stir, heat, add 0.3 part of diazoamino acid sodium when still temperature to be polymerized reaches 50 DEG C, stir 1h, then under 50 DEG C of polymerization temperatures, react 7 hours, add 0.4 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 80 parts, 0.4 part of styrenated phenol, 0.03 part of trialkyl ammonia chloride, stirring heating, under 70 DEG C of condensation temperatures, add 13 parts of sulfuric acid, at 70 DEG C, stirring is carried out slaking for 2 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 24.5, number-average molecular weight
viscosity 40(25 DEG C) PaS, functionality is close to 2.
Comparative example 4
Experiment condition, with embodiment 4, just not to latex grafting, namely directly adds terpine resin is modified in agglomeration process.Experimental result: combined styrene content 24.0, number-average molecular weight
viscosity 20(25 DEG C) PaS, functionality is close to 2.
Embodiment 5
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 60 DEG C, adds 0.4 part of Xylo-Mucine, and startup agitator is stirred to Xylo-Mucine and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 95 DEG C, add 0.4 part of terpine resin, be stirred to it and dissolve completely, then add 0.5 part of Xylo-Mucine dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 90 parts, water, styrene-butadiene latex 100 parts, 7 parts of disproportionated rosin soaps, 9 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 9 parts of modified terpene resins, stir, heat, add 0.3 part of diazoamino acid sodium when still temperature to be polymerized reaches 45 DEG C, stir 0.8h, then under 45 DEG C of polymerization temperatures, react 7 hours, add 0.3 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 80 parts, 0.4 part of styrenated phenol, 0.07 part of trialkyl ammonia chloride, stirring heating, under 60 DEG C of condensation temperatures, add 8 parts of sulfuric acid, at 60 DEG C, stirring is carried out slaking for 3 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 35(25 DEG C) PaS, functionality is close to 2.
Comparative example 5
Experiment condition is with embodiment 5, and just the unmodified terpine resin of latex grafting, adds the Xylo-Mucine of dissolving, after namely adding graft latex in condensing field, add the Xylo-Mucine of dissolving, then condense with embodiment 5 in agglomeration process.Experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 15(25 DEG C) PaS, functionality is close to 2.
Embodiment 6
1. the modification of terpine resin: in reaction flask, adds 100 parts of water, is heated to 80 DEG C, adds 0.5 part of sodium carboxymethylcellulose pyce, and startup agitator is stirred to sodium carboxymethylcellulose pyce and dissolves completely.In another reaction flask, add the ethanol of 100 parts of mass percent concentrations 75%, be heated to 85 DEG C, add 0.5 part of terpine resin, be stirred to it and dissolve completely, then add 0.3 part of sodium carboxymethylcellulose pyce dissolved, be uniformly mixed, obtained modified terpene resin.2. the preparation of graft latex: add 75 parts, water, styrene-butadiene latex 100 parts, 9 parts of disproportionated rosin soaps, 12 parts of tert-dodecyl mercaptans in polymeric kettle successively, after nitrogen replacement, add 10 parts of modified terpene resins, stir, heat, add 0.3 part of diazoamino acid sodium when still temperature to be polymerized reaches 35 DEG C, stir 1h, then under 35 DEG C of polymerization temperatures, react 7 hours, add 0.3 part of Sodium dimethyldithiocarbamate 40min, obtained graft latex.3. condense: get 100 parts of graft latexes and add condensing field, add WATER AS FLOW MEDIUM 60 parts, 0.3 part of styrenated phenol, 0.06 part of trialkyl ammonia chloride, stirring heating, under 50 DEG C of condensation temperatures, add 11 parts of sulfuric acid, at 50 DEG C, stirring is carried out slaking for 3 hours, is then obtained high-performance liquid styrene butadiene rubber through washing, dehydration, drying.Adopt classical way test sample, experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 30(25 DEG C) PaS, functionality is close to 2.
Comparative example 6
Experiment condition is with embodiment 6, and just the unmodified terpine resin of latex grafting, adds the Xylo-Mucine of dissolving, after namely adding graft latex in condensing field, add the Xylo-Mucine of dissolving, then condense with embodiment 6 in agglomeration process.Experimental result: combined styrene content 23.5, number-average molecular weight
viscosity 10(25 DEG C) PaS, functionality is close to 2.
Claims (12)
1. a preparation method for liquid styrene butadiene rubber, is characterized in that comprising the steps:
1) modification of terpine resin: in reaction flask, adding 100 parts of mass percent concentrations is the ethanol of 75%, be heated to 80 ~ 110 DEG C, add 0.1 ~ 0.6 part of terpine resin, startup agitator is stirred to it and dissolves completely, then add 0.1 ~ 0.5 part of cellulose ether aqueous solution, be uniformly mixed; Obtained modified terpene resin;
2) preparation of graft latex: add 50 ~ 150 parts, water, styrene-butadiene latex 100 parts, 2 ~ 10 parts of emulsifying agents, 5 ~ 15 parts of molecular weight regulators in polymeric kettle successively, after nitrogen replacement, add 5 ~ 15 parts of modified terpene resins, stir, heat, when still temperature to be polymerized reaches 30 ~ 60 DEG C, add 0.1 ~ 0.4 part of initiator, stir 0.8 ~ 1h, then under 30 ~ 60 DEG C of polymerization temperatures, react 5 ~ 8 hours, add 0.1 ~ 0.5 part of terminator, obtained graft latex;
3) condense: get 100 parts of graft latexes and add condensing field, add 20 ~ 100 parts of water, 0.2 ~ 0.5 part of anti-aging agent, stirring heating, under 20 ~ 80 DEG C of condensation temperatures, add 3 ~ 15 parts of flocculation agent, at 20 ~ 80 DEG C, stirring is carried out slaking for 1 ~ 3 hour, is then obtained liquid styrene butadiene rubber through washing, dehydration, drying.
2. preparation method as claimed in claim 1, is characterized in that described ether of cellulose is sodium carboxymethylcellulose pyce, Vltra tears sodium, Xylo-Mucine, sodium hydroxyethyl cellulose.
3. preparation method as claimed in claim 1, it is characterized in that described ether of cellulose is before adding terpine resin, dissolves in water, the mass ratio of the consumption of water and the add-on of ether of cellulose is 100 ︰ (0.1 ~ 0.8).
4. preparation method as claimed in claim 1, is characterized in that the add-on of terpine resin in 100 parts of ethanol is 0.2 ~ 0.4 part.
5. preparation method as claimed in claim 1, it is characterized in that in the modification procedure of terpine resin, the consumption of cellulose ether aqueous solution is 0.1 ~ 0.3 part.
6. preparation method as claimed in claim 1, it is characterized in that described emulsifying agent is disproportionated rosin soap, consumption is 4 ~ 6 parts.
7. preparation method as claimed in claim 1, is characterized in that described molecular weight regulator is selected from tert-dodecyl mercaptan, uncle ten carbon mercaptan, uncle 14 carbon mercaptan, uncle 16 carbon mercaptan.
8. preparation method as claimed in claim 1, it is characterized in that in the preparation process of described graft latex, the add-on of modified terpene resin is 5 ~ 10 parts.
9. preparation method as claimed in claim 1, is characterized in that in the preparation process of graft latex, and described initiator adopts diazoamino compound or persulphate.
10. preparation method as claimed in claim 1, is characterized in that described terminator is selected from Sodium dimethyldithiocarbamate 40min, quinhydrones.
11. preparation methods as claimed in claim 1, it is characterized in that in the preparation process of graft latex, polymerization temperature is 40 ~ 50 DEG C, reacts 5 ~ 8 hours.
12. preparation methods as claimed in claim 1, is characterized in that the condensation temperature of described graft latex is 20 ~ 30 DEG C.
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| CN103923357B (en) * | 2014-03-13 | 2016-04-06 | 中国热带农业科学院农产品加工研究所 | A kind of improve rubber crepe appearance color and keep all technical to reach the method for full milk glue |
| CN106032427B (en) * | 2015-03-18 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of rubber composition and vulcanized rubber and preparation method thereof |
| CN111032769B (en) * | 2017-09-01 | 2022-03-01 | 株式会社可乐丽 | Rubber composition for heavy duty tire and tire |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102998A (en) * | 1993-11-25 | 1995-05-31 | 李国良 | Aqueous emulsion type slurry of adhesive plaster |
| CN101104775A (en) * | 2007-08-15 | 2008-01-16 | 李国树 | Elastomer silicon rubber waterproofing paint |
| JP2009197082A (en) * | 2008-02-20 | 2009-09-03 | Bridgestone Corp | Adhesive composition |
| CN101935505A (en) * | 2010-08-31 | 2011-01-05 | 广州市安泰化学有限公司 | High elasto-plasticity waterproof caulking sealant used in outdoor and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102998A (en) * | 1993-11-25 | 1995-05-31 | 李国良 | Aqueous emulsion type slurry of adhesive plaster |
| CN101104775A (en) * | 2007-08-15 | 2008-01-16 | 李国树 | Elastomer silicon rubber waterproofing paint |
| JP2009197082A (en) * | 2008-02-20 | 2009-09-03 | Bridgestone Corp | Adhesive composition |
| CN101935505A (en) * | 2010-08-31 | 2011-01-05 | 广州市安泰化学有限公司 | High elasto-plasticity waterproof caulking sealant used in outdoor and preparation method thereof |
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