CN102199258A - Polyether modified silicon acrylic flexible resin and preparation method thereof - Google Patents
Polyether modified silicon acrylic flexible resin and preparation method thereof Download PDFInfo
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- CN102199258A CN102199258A CN 201110080094 CN201110080094A CN102199258A CN 102199258 A CN102199258 A CN 102199258A CN 201110080094 CN201110080094 CN 201110080094 CN 201110080094 A CN201110080094 A CN 201110080094A CN 102199258 A CN102199258 A CN 102199258A
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Abstract
The invention provides a polyether modified silicon acrylic flexible resin which comprises the following components in percentage by weight: 5-30% of polyether macromolecule emulsifier, 5-15% of vinyl siloxane, 0.1-4% of initiator, 30-70% of acrylate monomer, 0.5-2% of neutralizer and the balance of water. The preparation method comprises the following steps: copolymerizing the polyether macromolecule emulsifier used as a large monomer with the acrylate monomer in the presence of the vinyl siloxane and the initiator; and regulating the pH value with the neutralizer so as to obtain the resin. The resin provided by the invention has the advantages of good low-temperature flexibility, good water tolerance and excellent concrete permeability; and simultaneously, on one hand, the properties of the acrylic acid resin, such as bonding force, flexibility and the like, are obviously improved, and on the other hand, a core-shell structure can be formed in the resin through using a pre-emulsification semi-continuous dropwise adding mode. The resin in the invention can be widely applied to the fields of watertightness of buildings and the like and has an extremely wide application prospect.
Description
Technical field
The invention belongs to the resin material field, specifically be meant a kind of polyether-modified silicon third flexible resin and preparation method thereof.
Background technology
With vinyl monomers such as acrylate, vinylbenzene is main polymerization single polymerization monomer, the synthetic multipolymer is called the resin of acrylic acid series, since it have protect that look, look shallow, advantages such as Gao Guang, heat-resisting, weather-proof, corrosion-resistant and anti-pollution, be widely used in building, the industry of furniture, papermaking, printing and dyeing, wood working, industrial plastic and daily necessities.Acrylic resin mainly is divided into thermoplastic acrylic resin and thermosetting acrylic resin.Thermoplastic acrylic resin does not take place further crosslinked in film process, therefore its number-average molecular weight is bigger, have good guarantor's light tint retention, water-fast chemical resistant properties, fast drying, easy construction, the recoat and doing over again of being easy to construct, aligns at the whiteness of aluminium powder during the preparation aluminium powder paint.Thermoplastic acrylic resin is widely used in fields such as automobile, machinery, electrical equipment, buildings.But thermosetting acrylic resin is meant and has certain response type functional group in structure, resins such as the amino that when the system lacquer, passes through and add, epoxy, urethane, make its functional group participate in reaction to improve cross-linking density, the general relative molecular weight of thermosetting resin is lower.Thermosetting acrylic coating has excellent fullness ratio, solvent borne hardness, gloss, weather resisteant, nondiscoloration when high bake, brightness reversion not.Because the easy designability of acrylic resin prescription, the aqueous acrylic acid series cold coating is a pollution-free type coating with fastest developing speed in the water-borne coatings, that kind is maximum.Wherein the development of aqueous acrylic acid series cold coating and application start from the 1950's, have obtained developing rapidly to early 1970s.Compare with traditional solvent based coating, it is low, safe in utilization that water-borne coatings has price, saves the resource and the energy, reduces advantages such as environmental pollution and public hazards, thereby become the main direction of current development coatings industry.-along with the development of petrochemical technology, the price of vinylformic acid and esters monomer thereof descends significantly, has further promoted the development and application of acrylic resin coating variety.The development of external acrylic resin coating is very fast, has accounted for more than 40% of synthetic resins of coating at present.Its main type has: (1) solvent based coating; (2) photo-cured coating; (3) water-borne coatings mainly comprises thermoplasticity, the thermosetting coating of water-based; (4) high solid component coating and powder coating.
Summary of the invention
The objective of the invention is provides a kind of polyether-modified silicon third flexible resin according to above deficiency, and it has good bonding force, water tolerance and flexible characteristics.
The present invention is achieved through the following technical solutions: a kind of polyether-modified silicon third flexible resin, it is to be the polyethers macromolecule emulsifier of 5-30% by massfraction, massfraction is the vinylsiloxane of 5-15%, massfraction is the initiator of 0.1-4%, and massfraction is that the acrylate monomer of 30-70% and neutralizing agent prepared in reaction that massfraction is 0.5-2% obtain.
Described polyethers macromolecule emulsifier be by molecular weight in the polyether Glycols between the 200-2500 and acrylic or methacrylic acid under inhibitor action, the generation esterification obtains, and the mol ratio of described polyether Glycols and acrylic or methacrylic acid is 1: 1.2-1.8.
The present invention's technical scheme preferably is: also having added massfraction in above-mentioned reaction process is the sodium sulfonate emulsifying agent of 0.1-2%, and described sodium sulfonate emulsifying agent is that in Sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, di-isopropyl sodium naphthalene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, sodium lauryl sulphate, sodium laurylsulfonate, dioctyl sodium sulfosuccinate, allyloxy hydroxypropyl azochlorosulfonate acid sodium and the alkylamide vinyl sulfonic acid sodium one or more mix.
Described sodium sulfonate emulsifying agent be sodium lauryl sulphate and alkylamide vinyl sulfonic acid sodium by 1: 1 mixture of mass ratio, its add-on is 1%.
Described vinylsiloxane is a vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl trimethyl silane, γ-methacryloxy Trimethoxy silane, 3-methacryloxypropyl trimethyl silane, the triple phenoxyl vinyl silanes, vinyl three (2-methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide, 1-3 kind in 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane and the vinyl trichloro silane.
Described initiator is the 1-2 kind in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, tertbutyl peroxide, ammonium persulphate, ferrous salt, isopropyl benzene hydroperoxide, sodium bisulfite, Sulfothiorine, the rongalite.
Described acrylate monomer is a vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, the vinylformic acid n-propyl, Isooctyl acrylate monomer, lauryl acrylate, lauryl methacrylate(LMA), vinylbenzene, vinylformic acid stearyl alcohol ester, methacrylic acid stearyl alcohol ester, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate, acrylamide, senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, 2-5 kind in vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester and the methacrylic acid-β-hydroxypropyl acrylate.
Described neutralizing agent is at least a kind in ammoniacal liquor, triethylamine and the dimethylethanolamine.
The present invention's technical scheme preferably is: it is to be obtained by polyethers macromolecule emulsifier, vinylsiloxane, initiator, acrylate monomer and neutralizing agent prepared in reaction.Also added massfraction and be 1% sodium sulfonate emulsifying agent in above-mentioned reaction process, described sodium sulfonate emulsifying agent is that sodium lauryl sulphate and alkylamide vinyl sulfonic acid sodium are by 1: 1 mixture of mass ratio.Wherein, the massfraction of described polyethers macromolecule emulsifier is 7%, it be by molecular weight in the polyether Glycols between the 200-2500 and acrylic or methacrylic acid under inhibitor action, the generation esterification obtains, the mol ratio of polyether Glycols and acrylic or methacrylic acid is 1: 1.5, and stopper is the Resorcinol of the 0.1%-0.5% of acrylic or methacrylic acid quality.Described vinylsiloxane is that massfraction is 6% γ-methacryloxypropyl trimethoxy silane or vinyltrimethoxy silane.Described initiator is that massfraction is 1% Potassium Persulphate, ammonium persulphate or Diisopropyl azodicarboxylate.Described acrylate monomer is that massfraction is 32% vinylformic acid, methyl acrylate, methacrylic acid or methyl methacrylate.Described neutralizing agent is that massfraction is 1% ammoniacal liquor.All the other are 54% water.
A kind of method for preparing above-mentioned polyether-modified silicon third flexible resin, it be with the polyethers macromolecule emulsifier as big monomer, under vinylsiloxane and action of evocating,, and regulate with neutralizing agent and to obtain after the pH value with the acrylate monomer copolymerization.
The pre-emulsification of the nuclear layer monomer that includes polyethers macromolecule emulsifier and acrylate monomer is obtained examining pre-emulsion; The pre-emulsification of shell monomers that will include polyethers macromolecule emulsifier, vinylsiloxane and acrylate monomer again obtains the shell pre-emulsion; To examine then and drip initiator solution after pre-emulsion is warming up to 60-80 ℃, react after 2.5-5 hour to wherein dripping shell pre-emulsion and initiator solution, react again carry out after 2-5 hour that rear oxidation reduction is eliminated and adjust pH value with neutralizing agent after, filtration promptly obtains polyether-modified silicon third flexible resin of the present invention.
Polyether-modified silicon third flexible resin of the present invention is because the existence of polyether structure makes the resin that is synthesized have good low-temperature snappiness, water tolerance and excellent mixed earth perviousness.Simultaneously, owing to the introducing of polyethers macromolecule emulsifier and silicon class Acrylic Acid Monomer, the performances such as bonding force, water tolerance and snappiness of acrylic resin have been significantly improved.On the other hand, in the process of polyether-modified silicon third flexible resin of preparation, adopt the mode of the semicontinuous dropping of pre-emulsification, can make this resin formation nucleocapsid structure.Resin of the present invention can be widely used in fields such as buildings waterproof, has boundless application prospect.
Embodiment
Below further specify the present invention by specific embodiment:
Embodiment 1
With molecular weight is that 15 parts of addings of 0.6 part of 1 part of 432 parts in 1000 parts of polyether Glycols, vinylformic acid, KOH catalyzer, Resorcinol, dimethylbenzene of 300 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed Resorcinol and promptly obtained described polyethers macromolecule emulsifier 1 again.
682 parts of deionized waters are mixed the back stirring and dissolving with 32 parts of sodium lauryl sulphate, slowly drip the nuclear layer monomer mixed solution that includes 810 parts of butyl acrylates, 825 parts of vinylformic acid n-propyls, 510 parts of methyl methacrylates, 400 parts of polyethers macromolecule emulsifiers, 130 parts in vinylformic acid again, pre-then emulsification makes nuclear pre-emulsion 1 after 30 minutes standby.995 parts of deionized waters are mixed the back stirring and dissolving with 20 parts of sodium lauryl sulphate, slowly drip the shell monomers mixed solution that includes 700 parts of lauryl methacrylates, 535 parts of methyl methacrylates, 1075 parts of polyethers macromolecule emulsifiers, 970 parts of butyl acrylates, 670 parts of propenyl Trimethoxy silanes, 66 parts in vinylformic acid again, pre-then emulsification makes shell pre-emulsion 1 after 30 minutes standby.In the four-hole boiling flask that agitator, thermometer, prolong are housed, add 4500 parts of deionized waters, 13 parts of sodium lauryl sulphate, 10 parts of sodium bicarbonates, after stirring is warming up to 60 ℃, add 690 parts of nuclear pre-emulsions 1 and disperse to be warming up to 80 ℃ after 3 minutes, add the initiator solution of forming by 10 parts of Potassium Persulphates and 200 parts of deionized waters again and prepare seed.Treat that beginning to drip remaining nuclear pre-emulsion 1 after nothing obviously refluxes in solution turned blue and the reaction flask reaches by 10 parts of Potassium Persulphates and 800 parts of initiator solutions that deionized water is formed, control speed dripped off in 2 hours, dripping shell pre-emulsion 1 after being incubated 0.5 hour then reaches by 15 parts of Potassium Persulphates and 800 parts of initiator solutions that deionized water is formed, control speed dripped off in 4 hours, was incubated 1 hour then.Add 10 parts of tert-butyl peroxides after being cooled to 65 ℃ again and carry out redox and eliminate, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with ammoniacal liquor as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 1 of the present invention.
Embodiment 2
With molecular weight is that 10 parts of addings of 0.5 part of 0.8 part of 150 parts of 1000 parts of polyether Glycols, methacrylic acids, KOH catalyzer, MEHQ, dimethylbenzene of 1000 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 2 again.
650 parts of deionized waters are mixed the back stirring and dissolving with 30 parts of allyloxy hydroxypropyl azochlorosulfonate acid sodiums, slowly drip the nuclear layer monomer mixed solution that includes 750 parts of butyl acrylates, 785 parts of phenyl methacrylates, 420 parts of methyl methacrylates, 480 parts of polyethers macromolecule emulsifiers, 130 parts of methacrylic acids again, pre-then emulsification makes nuclear pre-emulsion 2 after 30 minutes standby.100 parts of deionized waters are mixed the back stirring and dissolving with 30 parts of sodium lauryl sulphate, slowly drip the shell monomers mixed solution that includes 680 parts of ethyl propenoates, 390 parts of methyl methacrylates, 1100 parts of polyethers macromolecule emulsifiers, 990 parts of butyl acrylates, 620 parts of γ-methacryloxypropyl trimethoxy silane, 200 parts of vinyl trichloro silanes, 70 parts in vinylformic acid again, pre-then emulsification makes shell pre-emulsion 2 after 30 minutes standby.In the four-hole boiling flask that agitator, thermometer, prolong are housed, add 4500 parts of deionized waters, 20 parts of allyloxy hydroxypropyl azochlorosulfonate acid sodiums, 10 parts of sodium bicarbonates, after stirring is warming up to 60 ℃, add 720 parts of nuclear pre-emulsions 2 and disperse to be warming up to 80 ℃ after 3 minutes, add the initiator solution of forming by 13 parts of ammonium persulphates and 180 parts of deionized waters again and prepare seed.Treat that beginning to drip remaining nuclear pre-emulsion 2 after nothing obviously refluxes in solution turned blue and the reaction flask reaches by 11 parts of Potassium Persulphates and 820 parts of initiator solutions that deionized water is formed, control speed dripped off in 4 hours, dripping shell pre-emulsion 2 after being incubated 1 hour then reaches by 15 parts of Potassium Persulphates and 810 parts of initiator solutions that deionized water is formed, control speed dripped off in 1.5 hours, was incubated 0.5 hour then.Add 9 parts of rongalite after being cooled to 65 ℃ again and carry out redox and eliminate, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with triethylamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 2 of the present invention.
Embodiment 3
With molecular weight is that 10 parts of addings of 0.7 part of 0.8 part of 500 parts in 800 parts of polyether Glycols, vinylformic acid, KOH catalyzer, MEHQ, dimethylbenzene of 200 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 3 again.
700 parts of deionized waters are mixed the back stirring and dissolving with 25 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, slowly drip the nuclear layer monomer mixed solution that includes 800 parts of butyl acrylates, 770 parts of lauryl methacrylate(LMA)s, 310 parts of methyl methacrylates, 650 parts of polyethers macromolecule emulsifiers, 110 parts of methacrylic acids again, pre-then emulsification makes nuclear pre-emulsion 3 after 30 minutes standby.100 parts of deionized waters are mixed the back stirring and dissolving with 26 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, slowly drip the shell monomers mixed solution that includes 750 parts of Isooctyl acrylate monomers, 340 parts of methyl methacrylates, 850 parts of polyethers macromolecule emulsifiers, 1010 parts of butyl acrylates, 850 parts of vinyltrimethoxy silanes, 80 parts of methacrylic acids again, pre-then emulsification makes shell pre-emulsion 3 after 30 minutes standby.In the four-hole boiling flask that agitator, thermometer, prolong are housed, add 4500 parts of deionized waters, 25 parts of alkene disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, 12 parts of sodium bicarbonates, after stirring is warming up to 60 ℃, add 750 parts of nuclear pre-emulsions 3 and disperse to be warming up to 80 ℃ after 3 minutes, add the initiator solution of forming by 12 parts of ammonium persulphates and 200 parts of deionized waters again and prepare seed.Treat that beginning to drip remaining nuclear pre-emulsion 3 after nothing obviously refluxes in solution turned blue and the reaction flask reaches by 15 parts of ammonium persulphates and 800 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, dripping shell pre-emulsion 3 after being incubated 1 hour then reaches by 13 parts of Potassium Persulphates and 850 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, was incubated 1 hour then.13 parts of tertbutyl peroxides of adding and 10 parts of rongalite carry out the redox elimination after being cooled to 65 ℃ again, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 3 of the present invention.
Embodiment 4
With molecular weight is that 14 parts of addings of 0.8 part of 1.2 parts of 330 parts in 1200 parts of polyether Glycols, vinylformic acid, KOH catalyzer, MEHQ, dimethylbenzene of 400 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 4 again.
700 parts of deionized waters are mixed the back stirring and dissolving with 25 parts of sodium laurylsulfonates, slowly drip the nuclear layer monomer mixed solution that includes 600 parts of butyl acrylates, 200 parts of ethyl propenoates, 770 parts of lauryl methacrylate(LMA)s, 250 parts of methyl methacrylates, 690 parts of polyethers macromolecule emulsifiers, 150 parts of methacrylic acids again, pre-then emulsification makes nuclear pre-emulsion 4 after 30 minutes standby.100 parts of deionized waters are mixed the back stirring and dissolving with 26 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, slowly drip the shell monomers mixed solution that includes 850 parts of Isooctyl acrylate monomers, 300 parts of methyl methacrylates, 900 parts of polyethers macromolecule emulsifiers, 1050 parts of vinylformic acid 9 butyl esters, 810 parts of vinyltrimethoxy silanes, 50 parts of methacrylic acids again, pre-then emulsification makes shell pre-emulsion 4 after 30 minutes standby.In the four-hole boiling flask that agitator, thermometer, prolong are housed, add 4500 parts of deionized waters, 25 parts of alkene sodium laurylsulfonates, 11 parts of sodium bicarbonates, after stirring is warming up to 60 ℃, add 750 parts of nuclear pre-emulsions 4 and disperse to be warming up to 80 ℃ after 3 minutes, add the initiator solution of forming by 15 parts of ammonium persulphates and 200 parts of deionized waters again and prepare seed.Treat that beginning to drip remaining nuclear pre-emulsion 4 after nothing obviously refluxes in solution turned blue and the reaction flask reaches by 16 parts of ammonium persulphates and 800 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, dripping shell pre-emulsion 4 after being incubated 1 hour then reaches by 17 parts of Potassium Persulphates and 850 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, was incubated 1 hour then.12 parts of tertbutyl peroxides of adding and 11 parts of rongalite carry out the redox elimination after being cooled to 65 ℃ again, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 4 of the present invention.
Embodiment 5
With molecular weight is that 15 parts of addings of 1.2 parts of 1 part of 105 parts of 1500 parts of polyether Glycols, methacrylic acids, KOH catalyzer, MEHQ, dimethylbenzene of 2000 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 5 again.
800 parts of deionized waters are mixed the back stirring and dissolving with 28 parts of dioctyl sodium sulfosuccinates, slowly drip the nuclear layer monomer mixed solution that includes 1000 parts of butyl acrylates, 770 parts of lauryl methacrylate(LMA)s, 350 parts of methyl acrylates, 700 parts of polyethers macromolecule emulsifiers, 120 parts in vinylformic acid again, pre-then emulsification makes nuclear pre-emulsion 5 after 30 minutes standby.100 parts of deionized waters are mixed the back stirring and dissolving with 25 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, slowly drip the shell monomers mixed solution that includes 850 parts of Isooctyl acrylate monomers, 400 parts of methyl methacrylates, 900 parts of polyethers macromolecule emulsifiers, 1150 parts of butyl acrylates, 800 parts in vinyl three (2-methoxy ethoxy) silane, 85 parts of methacrylic acids again, pre-then emulsification makes shell pre-emulsion 5 after 30 minutes standby.In the four-hole boiling flask that agitator, thermometer, prolong are housed, add 4500 parts of deionized waters, 23 parts of dioctyl sodium sulfosuccinates, 12 parts of sodium bicarbonates, after stirring is warming up to 60 ℃, add 750 parts of nuclear pre-emulsions 5 and disperse to be warming up to 80 ℃ after 3 minutes, add the initiator solution of forming by 12 parts of ammonium persulphates and 200 parts of deionized waters again and prepare seed.Treat that beginning to drip remaining nuclear pre-emulsion 5 after nothing obviously refluxes in solution turned blue and the reaction flask reaches by 15 parts of ammonium persulphates and 800 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, dripping shell pre-emulsion 5 after being incubated 1 hour then reaches by 16 parts of Potassium Persulphates and 850 parts of initiator solutions that deionized water is formed, control speed dripped off in 3 hours, was incubated 1 hour then.12 parts of tertbutyl peroxides of adding and 11 parts of rongalite carry out the redox elimination after being cooled to 65 ℃ again, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 5 of the present invention.
Embodiment 6
With molecular weight is that 15 parts of addings of 1.2 parts of 1 part of 48 parts in 2000 parts of polyether Glycols, vinylformic acid, KOH catalyzer, MEHQ, dimethylbenzene of 2500 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 6 again.
With deionized water and massfraction is that 0.2% sodium lauryl sulphate is mixed the back stirring and dissolving, slowly dripping and including massfraction is 10% butyl acrylate, lauryl methacrylate(LMA), methyl acrylate, massfraction is that 3% polyethers macromolecule emulsifier 6, massfraction are acrylic acid nuclear layer monomer mixed solution of 6%, and pre-then emulsification makes nuclear pre-emulsion 6 after 30 minutes standby.With deionized water and massfraction is that 0.5% alkylamide vinyl sulfonic acid sodium mixes the back stirring and dissolving, slowly dripping and including massfraction is 10% Isooctyl acrylate monomer, methyl methacrylate, massfraction is 4% polyethers macromolecule emulsifier 6, massfraction is 6% vinyl three (2-methoxy ethoxy) silane, massfraction is the shell monomers mixed solution of 6% methacrylic acid, and pre-then emulsification makes shell pre-emulsion 6 after 30 minutes standby.The adding massfraction is that 0.3% sodium lauryl sulphate, massfraction are 0.5% sodium bicarbonate and deionized water in the four-hole boiling flask that agitator, thermometer, prolong are housed, after stirring is warming up to 60 ℃, add nuclear pre-emulsion 6 and also disperse to be warming up to 80 ℃ after 3 minutes, adding by massfraction is that the initiator solution that 0.2% ammonium persulphate and deionized water are formed prepares seed again.Treat not have in solution turned blue and the reaction flask and begin to drip remaining nuclear pre-emulsion 6 after obviously refluxing and be the initiator solution that 0.2% ammonium persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, be incubated then after 1 hour and drip shell pre-emulsion 6 and be the initiator solution that 0.1% Potassium Persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, was incubated 1 hour then.Add tertbutyl peroxide and rongalite after being cooled to 65 ℃ again and carry out the redox elimination, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 6 of the present invention.
Embodiment 7
With molecular weight is that 15 parts of addings of 1.2 parts of 1 part of 48 parts in 2000 parts of polyether Glycols, vinylformic acid, KOH catalyzer, MEHQ, dimethylbenzene of 2500 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 7 again.
With deionized water and massfraction is that 0.05% sodium lauryl sulphate is mixed the back stirring and dissolving, slowly dripping and including massfraction is 25% butyl acrylate, lauryl methacrylate(LMA), methyl acrylate, massfraction is that 2% polyethers macromolecule emulsifier 7, massfraction are acrylic acid nuclear layer monomer mixed solution of 10%, and pre-then emulsification makes nuclear pre-emulsion 7 after 30 minutes standby.With deionized water and massfraction is that 0.5% alkylamide vinyl sulfonic acid sodium mixes the back stirring and dissolving, slowly dripping and including massfraction is 25% Isooctyl acrylate monomer, methyl methacrylate, massfraction is 3% polyethers macromolecule emulsifier 7, massfraction is 5% vinyl three (2-methoxy ethoxy) silane, massfraction is the shell monomers mixed solution of 10% methacrylic acid, and pre-then emulsification makes shell pre-emulsion 7 after 30 minutes standby.The adding massfraction is that 0.05% sodium lauryl sulphate, massfraction are 1% sodium bicarbonate and deionized water in the four-hole boiling flask that agitator, thermometer, prolong are housed, after stirring is warming up to 60 ℃, add nuclear pre-emulsion 7 and also disperse to be warming up to 80 ℃ after 3 minutes, adding by massfraction is that the initiator solution that 0.04% ammonium persulphate and deionized water are formed prepares seed again.Treat not have in solution turned blue and the reaction flask and begin to drip remaining nuclear pre-emulsion 7 after obviously refluxing and be the initiator solution that 0.03% ammonium persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, be incubated then after 1 hour and drip shell pre-emulsion 7 and be the initiator solution that 0.03% Potassium Persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, was incubated 1 hour then.Add tertbutyl peroxide and rongalite after being cooled to 65 ℃ again and carry out the redox elimination, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 7 of the present invention.
Embodiment 8
With molecular weight is that 15 parts of addings of 1.2 parts of 1 part of 48 parts in 2000 parts of polyether Glycols, vinylformic acid, KOH catalyzer, MEHQ, dimethylbenzene of 2500 are equipped with thermometer, prolong, water trap, are had in the four-hole reaction flask of stirring, be warming up to 80-120 ℃, start stirring, temperature is elevated to insulation reaction when occurring refluxing, when slowly being warmed up to the acid number of surveying≤5mgKOH/g again, stopped reaction, vacuum is extracted reflux solvent dimethylbenzene out, and underpressure distillation is removed MEHQ and promptly obtained described polyethers macromolecule emulsifier 8 again.
With deionized water and massfraction is that 1% sodium lauryl sulphate is mixed the back stirring and dissolving, slowly dripping and including massfraction is 10% butyl acrylate, lauryl methacrylate(LMA), methyl acrylate, massfraction is that 15% polyethers macromolecule emulsifier 8, massfraction are acrylic acid nuclear layer monomer mixed solution of 5%, and pre-then emulsification makes nuclear pre-emulsion 8 after 30 minutes standby.With deionized water and massfraction is that 0.7% alkylamide vinyl sulfonic acid sodium mixes the back stirring and dissolving, slowly dripping and including massfraction is 10% Isooctyl acrylate monomer, methyl methacrylate, massfraction is 15% polyethers macromolecule emulsifier 8, massfraction is 15% vinyl three (2-methoxy ethoxy) silane, massfraction is the shell monomers mixed solution of 5% methacrylic acid, and pre-then emulsification makes shell pre-emulsion 8 after 30 minutes standby.The adding massfraction is that 0.3% sodium lauryl sulphate, massfraction are 0.5% sodium bicarbonate and deionized water in the four-hole boiling flask that agitator, thermometer, prolong are housed, after stirring is warming up to 60 ℃, add nuclear pre-emulsion 8 and also disperse to be warming up to 80 ℃ after 3 minutes, adding by massfraction is that the initiator solution that 2% ammonium persulphate and deionized water are formed prepares seed again.Treat not have in solution turned blue and the reaction flask and begin to drip remaining nuclear pre-emulsion 8 after obviously refluxing and be the initiator solution that 1% ammonium persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, be incubated then after 1 hour and drip shell pre-emulsion 8 and be the initiator solution that 1% Potassium Persulphate and deionized water are formed by massfraction, control speed dripped off in 3 hours, was incubated 1 hour then.Add tertbutyl peroxide and rongalite after being cooled to 65 ℃ again and carry out the redox elimination, drip off back insulation 30 minutes, cooling is also adjusted pH value to 8 with dimethylethanolamine as neutralizing agent, and filtration promptly obtains polyether-modified silicon third flexible resin 8 of the present invention.
Claims (10)
1. polyether-modified silicon third flexible resin, it is to be the polyethers macromolecule emulsifier of 5-30% by massfraction, massfraction is the vinylsiloxane of 5-15%, massfraction is the initiator of 0.1-4%, massfraction is that the acrylate monomer of 30-70% and neutralizing agent prepared in reaction that massfraction is 0.5-2% obtain, and surplus is a water.
2. polyether-modified silicon third flexible resin according to claim 1, it is characterized in that: described polyethers macromolecule emulsifier be by molecular weight in the polyether Glycols between the 200-2500 and acrylic or methacrylic acid under inhibitor action, the generation esterification obtains, and the mol ratio of described polyether Glycols and acrylic or methacrylic acid is 1: 1.2-1.8.
3. polyether-modified silicon third flexible resin according to claim 1, it is characterized in that: comprise that also massfraction is the sodium sulfonate emulsifying agent of 0.1-2% in the raw material of described polyether-modified silicon third flexible resin, described sodium sulfonate emulsifying agent is that in Sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, di-isopropyl sodium naphthalene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, sodium lauryl sulphate, sodium laurylsulfonate, dioctyl sodium sulfosuccinate, allyloxy hydroxypropyl azochlorosulfonate acid sodium and the alkylamide vinyl sulfonic acid sodium one or more mix.
4. polyether-modified silicon third flexible resin according to claim 3 is characterized in that: described sodium sulfonate emulsifying agent be sodium lauryl sulphate and alkylamide vinyl sulfonic acid sodium by 1: 1 mixture of mass ratio, its add-on is 1%.
5. polyether-modified silicon third flexible resin according to claim 1 is characterized in that: described vinylsiloxane is a vinyltrimethoxy silane, vinyltriethoxysilane, the propenyl trimethyl silane, γ-methacryloxy Trimethoxy silane, 3-methacryloxypropyl trimethyl silane, the triple phenoxyl vinyl silanes, vinyl three (2-methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, vinyl silane triisopropoxide, 1-3 kind in 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane and the vinyl trichloro silane.
6. polyether-modified silicon third flexible resin according to claim 1 is characterized in that: described initiator is the 1-2 kind in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, tertbutyl peroxide, ammonium persulphate, ferrous salt, isopropyl benzene hydroperoxide, sodium bisulfite, Sulfothiorine, the rongalite.
7. polyether-modified silicon third flexible resin according to claim 1 is characterized in that: described acrylate monomer is a vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, the vinylformic acid n-propyl, Isooctyl acrylate monomer, lauryl acrylate, lauryl methacrylate(LMA), vinylformic acid stearyl alcohol ester, methacrylic acid stearyl alcohol ester, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate, acrylamide, senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, 2-5 kind in vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester and the methacrylic acid-β-hydroxypropyl acrylate.
8. polyether-modified silicon third flexible resin according to claim 1 is characterized in that: described neutralizing agent is at least a kind in ammoniacal liquor, triethylamine and the dimethylethanolamine.
9. method for preparing described polyether-modified silicon third flexible resin of claim 1, it is characterized in that: described polyether-modified silicon third flexible resin is as big monomer with the polyethers macromolecule emulsifier, under vinylsiloxane and action of evocating, with the acrylate monomer copolymerization, and regulate with neutralizing agent and to obtain after the pH value.
10. the preparation method of polyether-modified silicon third flexible resin according to claim 9, it is characterized in that: the pre-emulsification of nuclear layer monomer that will include polyethers macromolecule emulsifier and acrylate monomer obtains examining pre-emulsion; The pre-emulsification of shell monomers that will include polyethers macromolecule emulsifier, vinylsiloxane and acrylate monomer again obtains the shell pre-emulsion; To examine then and drip initiator solution after pre-emulsion is warming up to 60-80 ℃, react after 2.5-5 hour to wherein dripping shell pre-emulsion and initiator solution, react again carry out after 2-5 hour that rear oxidation reduction is eliminated and adjust pH value with neutralizing agent after, filtration promptly obtains polyether-modified silicon third flexible resin of the present invention.
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| CN104829161A (en) * | 2015-04-02 | 2015-08-12 | 安徽建筑大学 | Novel waterproof agent for building gypsum, and preparation method thereof |
| CN106234340A (en) * | 2016-08-04 | 2016-12-21 | 苏州灵垦农业科技有限公司 | A kind of wear-resistant intelligentized pesticide spraying machine people |
| CN106866981A (en) * | 2017-03-08 | 2017-06-20 | 东莞市贝杰化工有限公司 | Hydroxylated acrylic resin and cured film |
| CN110982018A (en) * | 2019-12-04 | 2020-04-10 | 杭州传化精细化工有限公司 | Silane-modified high-molecular stabilizer and preparation method and application thereof |
| CN117209675A (en) * | 2023-09-14 | 2023-12-12 | 佛山市三水协佳化工有限公司 | Flexible acrylic ester and preparation method thereof |
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| CN101649018A (en) * | 2009-09-15 | 2010-02-17 | 武汉力诺化学集团有限公司 | Preparation method of fluorinated hydroxy vinyl tertcarbonate-acrylate copolymer soap-free emulsion with core-shell structure |
| CN101798369A (en) * | 2010-03-05 | 2010-08-11 | 北京高盟新材料股份有限公司 | Silicone-acrylic emulsion with high silicon content and preparation method thereof |
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| CN1557850A (en) * | 2004-02-13 | 2004-12-29 | 杨慕杰 | Process for preparing organosilicon modified acrylic ester elastic emulsion |
| CN101649018A (en) * | 2009-09-15 | 2010-02-17 | 武汉力诺化学集团有限公司 | Preparation method of fluorinated hydroxy vinyl tertcarbonate-acrylate copolymer soap-free emulsion with core-shell structure |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104829161A (en) * | 2015-04-02 | 2015-08-12 | 安徽建筑大学 | Novel waterproof agent for building gypsum, and preparation method thereof |
| CN106234340A (en) * | 2016-08-04 | 2016-12-21 | 苏州灵垦农业科技有限公司 | A kind of wear-resistant intelligentized pesticide spraying machine people |
| CN106866981A (en) * | 2017-03-08 | 2017-06-20 | 东莞市贝杰化工有限公司 | Hydroxylated acrylic resin and cured film |
| CN106866981B (en) * | 2017-03-08 | 2020-06-19 | 东莞市贝杰化工有限公司 | Hydroxy acrylic resin and cured film |
| CN110982018A (en) * | 2019-12-04 | 2020-04-10 | 杭州传化精细化工有限公司 | Silane-modified high-molecular stabilizer and preparation method and application thereof |
| CN117209675A (en) * | 2023-09-14 | 2023-12-12 | 佛山市三水协佳化工有限公司 | Flexible acrylic ester and preparation method thereof |
| CN117209675B (en) * | 2023-09-14 | 2024-04-12 | 广东协佳化学有限公司 | Flexible acrylic ester and preparation method thereof |
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