CN1085931A - The rubber static flocking production method of binding agent - Google Patents
The rubber static flocking production method of binding agent Download PDFInfo
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- CN1085931A CN1085931A CN 92112380 CN92112380A CN1085931A CN 1085931 A CN1085931 A CN 1085931A CN 92112380 CN92112380 CN 92112380 CN 92112380 A CN92112380 A CN 92112380A CN 1085931 A CN1085931 A CN 1085931A
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Abstract
The present invention is a kind of method of producing the rubber static flocking with binding agent.At first be that partial monosomy is emulsifiable in the deionized water, add the part initiator, the polymerization under agitation that heats up generates in " seed ", and then residual monomers and initiator at the uniform velocity be added dropwise to reactor, make it aggregate into " shell " at " seed " outside surface, behind the insulation certain hour, cooling, add auxiliary agent, stir, filter, obtain product.
Description
The present invention is a kind of production method of binding agent, the production method of the binding agent of using on a kind of rubber static flocking of further saying so.
Rubber static flocking binding agent as synthetic rubber, Resins, epoxy, urethane, Synolac etc., mainly adopted solvent method synthetic in the past.Production method generally is: product is made in monomer dissolving-mixing-heated polymerizable-filtration-allotment.Adopt solvent method synthetic binding agent to be called the solvent-borne type binding agent.The solvent-borne type binding agent generally need use as N-BUTYL ACETATE, acetone, dimethylbenzene equal solvent and be medium, so there is inflammable, explosive, poisonous operation, shortcoming such as fire hazardous in electrostatic field particularly, add the cost height, its use range descends year by year, and is progressively replaced by the water-latex type binding agent.The water-latex type binding agent, as styrene-propene acid copolymer and Vinyl Acetate Copolymer etc., normally binary or terpolymer are that monomer is emulsifiable in the water, mix or dropping, polyreaction in heat-processed waits operation to make product after filtration.For example: system water-latex type Vinyl Acetate Copolymer type binding agent, can be earlier emulsifiers dissolve in water, add initiator after, and drip adds monomer, makes the abundant polymerization of monomer; Keep temperature of reaction about 70 ℃ by refluxing; After reaction finishes, continue insulation one hour, to reduce residual monomer content, cooling obtains uniform polyvinyl acetate after filtration then, is commonly called as " white glues ".But at present binary of producing or ternary water-latex type binding agent exist rubber surface be difficult for wetting, shortcoming such as cohesive force is low, and is not wear-resisting.So the water-latex type binding agent still needs further to improve.
At the problems referred to above, at the high request that on rubber substrate, carries out static flocking, the present invention proposes the technological line of emulsified acrylic acid ester multi-component copolymer, say so in more detail with partial monosomy at first the emulsification post polymerization become " seed ", then another part monomer is aggregated into " shell " again at the outside surface of " seed ", make product at last.
The present invention at first adds a certain amount of catalysis initiator with the polymerization after the part emulsification with monomer, the intensification polymerization, after treating that " seed " forms, drip the remainder polymerization within a certain period of time, make their outside surface polymerizations at " seed " with monomer, catalysis initiator and emulsifying agent, form the superpolymer of " shell ", particle is grown up gradually, dropwise, continue the insulation certain hour, cool off, add auxiliary agent, filtration then, obtain rubber static flocking binding agent.
Can be a lot of as the monomeric species that the present invention uses, have that butyl acrylate, ethyl propenoate, vinylbenzene, propylene are fine, vinyl acetate between to for plastic, vinylformic acid, n-methylolacrylamide, methacrylic acid, etherificate n-methylolacrylamide, methacryloyl epoxy ester, melamine, formaldehyde etc.These monomers can be divided into soft monomer, rigid monomer, reactive monomer or self-cross linking monomer again.Soft monomer is that a class contains-monomer of ROOR ' group, and wherein R can be the alkyl that contains 3C～8C, and R ' can be the alkyl that contains 2C～8C, and soft monomer shared ratio in polymkeric substance is 60～80%.Rigid monomer is that a class contains-monomer of R-C=C-R '-group, and wherein R can be alkyl or the aromatics that contains 3C～8C, and R ' can be alkyl or the cyano group that contains 2C～4C, and the shared ratio of rigid monomer is 15～30% in polymkeric substance.Self-cross linking monomer be a class contain-R-COOH or-monomer of R-CONH group, wherein R can be the alkyl that contains 2C～10C, self-cross linking monomer shared ratio in polymkeric substance is 1～10%.
Monomer with 10～40% such as butyl acrylate, ethyl propenoate, melamine, vinylbenzene, propylene are fine, vinyl acetate between to for plastic, vinylformic acid, n-methylolacrylamide, methacrylic acid, add emulsifying agent, carry out emulsification.After the emulsification, monomer is moved in the polymeric kettle, adds 75～98% the catalysis initiator account for the initiator total amount, be warming up to 60 ℃, under whipped state, carry out polymerization, generate gradually in " seed ", should " seed " promptly as " core " of final copolymer.After treating that " seed " forms, remaining emulsified monomer and catalysis initiator at the uniform velocity are added dropwise to polymeric kettle under 70 ℃ of stirrings, continue to stir and be incubated 0.5～2.0 hour.The monomer that the back dropping is entered in the outside surface polymerization of " seed ", forms the superpolymer of " shell ", and particle is grown up gradually.Because the rate of growth that " seed " particle is little is very fast, the rate of growth that " seed " particle is big is slower, end-result, and the particle of multipolymer is tending towards being evenly distributed.
The used emulsifying agent of the present invention is a kind of mixed emulsifier, be sodium salt, with the peregal of nonionic surface active agent such as Fatty Alcohol(C12-C14 and C12-C18) ethylene oxide condensate, the OP-10 of alkylphenol ethylene oxide condensate, composite the forming such as Si Pan-60 of anhydrous sorbitol olein by alkane such as aniorfic surfactant such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonatees.Its consumption is 2.0～4.0% of a polymkeric substance total amount, and wherein the ratio of anionic and nonionic surface active agent is 3～7: 1.
The catalysis initiator that the present invention adopts refers to if persulphate, as the redox system of ammonium persulphate, Potassium Persulphate and persulphate and sulphite.The consumption of initiator reacts not exclusively very little, and residual monomer is many, and consumption is too many, and reaction is too fierce, produces more implode thing, and therefore originally its consumption of bright control is in the scope of polymkeric substance 0.1～3.0%.
After the polyreaction, cool off, add 2.0～3.0% the auxiliary agent six hydroxyl hydrogen urea formaldehydes that account for the polymkeric substance total amount, stir, filter, can obtain product of the present invention.
The present invention adopts step-by-step polymerization, multi-component copolymer, and the binding agent that the operational path of compound emulsifying agent makes is used for static flocking on the rubber substrate, has advantages such as bonding force height, wear-resisting wiping, nuisanceless, no quick-fried, combustion danger.
Example 1
(1) gets deionized water 250 grams, add emulsifier sodium lauryl sulfate 13 grams, OP emulsifying agent (alkylphenol ethylene oxide condensate) 2.4 grams, add monomer vinylformic acid 5.0 grams after the stirring and dissolving, butyl acrylate 125 grams, fine 30 grams of propylene, vinylbenzene 10 grams, methyl methacrylate 4.5 grams, fully emulsified.
(2) add deionized water 250 and restrain in the reactor, put into the emulsion for preparing again, add 1.0% initiator ammonium persulfate 10 grams of total amount, stir and be warmed up to 60 ℃ of reactions, carry out preliminary polymerization, form " seed " body.
(3) heating rises to 70 ℃, drips the mix monomer of being made up of following ratio continuously:
Fine 11 grams of vinylformic acid 5 gram butyl acrylates, 210 gram propylene
Methyl methacrylate 6.1 gram n-methylolacrylamide 11 grams
The control rate of addition was 250 gram/times, add 0.5 gram initiator ammonium persulfate after adding, be incubated 30 minutes, benefit adds water to 1000 grams, cooling then adds auxiliary agent six hydroxyl hydrogen urea formaldehydes 12 grams, adjusts viscosity with ammonia, make rubber static flocking binding agent after filtration, its wear resistance can reach more than 10000 times.
Example 2
(1) deionized water 250 grams, add emulsifying agent Sodium dodecylbenzene sulfonate 10 grams, emulsifying agent alkylphenol ethylene oxide condensate 2.2 grams, add melamine 20 grams after the stirring and dissolving, formaldehyde 4 grams add monomer butyl acrylate 18 grams again, fine 5 grams of propylene, vinylformic acid 15 grams, ethyl propenoate 30 grams, vinylbenzene 1.0 gram emulsifications.
(2) deionized water 250 grams place reactor, add the emulsion for preparing again, add 0.15% initiator potassium persulfate, 1.5 grams of total amount, stir and are warming up to 60 ℃ of reactions, carry out preliminary polymerization, form " seed " body.
(3) heat temperature raising rises to 70 ℃, drips the mixed monomer of being made up of following ratio continuously:
Vinylformic acid 4.5 gram butyl acrylates 172 gram ethyl propenoates 80 grams
The fine 29 gram vinylbenzene of propylene 30 grams
The control rate of addition was 200 gram/times, add 0.5 gram initiator potassium persulfate after adding, be incubated 30 minutes, benefit adds water to 1000 grams, be warmed up to 90 ℃ of half an hour again, be cooled to room temperature, add auxiliary agent six hydroxyl hydrogen urea formaldehydes 12 grams, adjust pH value and viscosity with ammonia, make after filtration the rubber static flocking with binding agent, wear-resisting, water-fast, fastness is good.
Example 3
Adopt monomer and the prescription and the operation of example 1, use the emulsifying agent alkylphenol ethylene oxide condensates of 3.8 grams and the initiator ammonium persulfates of 11.4 gram sodium lauryl sulphate and 2 grams, make rubber static through polyreaction and plant and use the suede binding agent.
Example 4
Adopt monomer and the prescription and the operation of example 2, use the initiator potassium persulfate of emulsifying agent Sodium dodecylbenzene sulfonate and the 5 gram alkylphenol ethylene oxide condensates and 5 grams of 15 grams, make rubber static flocking binding agent through polymerization.
Claims (4)
1, a kind of rubber static flocking production method of binding agent, be that monomer is emulsifiable in the deionized water, add persulfate initiator, polymerization, it is characterized in that 10～40% monomer is added the composite emulsifying agent of anionic and nonionic surface active agent to carry out fully emulsified in deionized water, move into and to add 75～98% the initiator that accounts for the initiator total amount in the reactor, be warming up to polymerization under 60 ℃ of stirrings, generate in " seed ", under 70 ℃ of stirrings, at the uniform velocity splash in the reactor residual monomers and initiator then, make its outside surface aggregate into the superpolymer of " shell " at " seed ", dripped follow-up continuation of insurance temperature 0.5～2 hour, cooling adds 2.0～3.0% the auxiliary agent six hydroxyl hydrogen urea formaldehydes account for the polymkeric substance total amount, and after-filtration stirs.
2, a kind of the method for claim 1, it is characterized in that said monomer be contain-the soft monomer of ROOR ' group accounts for 60～80% in polymkeric substance, contain-R-C=C-R '-the rigid monomer of group accounts for 15～30% in polymkeric substance, contain-R-COOH or-self-cross linking monomer of R-CONH group accounts for 1～10% in polymkeric substance.
3, a kind of the method for claim 1, it is characterized in that said emulsifying agent be anionic and nonionic surface active agent with 3～7: 1 ratio is composite to form, and its consumption is 2.0～4.0% of a polymkeric substance total amount.
4, a kind of the method for claim 1 is characterized in that said initiator is an ammonium persulphate, and Potassium Persulphate, its consumption are 0.1～3.0% of polymkeric substance total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112380 CN1085931A (en) | 1992-10-19 | 1992-10-19 | The rubber static flocking production method of binding agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112380 CN1085931A (en) | 1992-10-19 | 1992-10-19 | The rubber static flocking production method of binding agent |
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| Publication Number | Publication Date |
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| CN1085931A true CN1085931A (en) | 1994-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92112380 Pending CN1085931A (en) | 1992-10-19 | 1992-10-19 | The rubber static flocking production method of binding agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038192C (en) * | 1994-05-03 | 1998-04-29 | 北京联合大学化学工程学院 | Electrostatic flocking adhesives solidifying under normal temperature |
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1992
- 1992-10-19 CN CN 92112380 patent/CN1085931A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038192C (en) * | 1994-05-03 | 1998-04-29 | 北京联合大学化学工程学院 | Electrostatic flocking adhesives solidifying under normal temperature |
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