CN104774287A - Polyacrylate emulsion microgel and preparation method thereof - Google Patents
Polyacrylate emulsion microgel and preparation method thereof Download PDFInfo
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- CN104774287A CN104774287A CN201510108457.9A CN201510108457A CN104774287A CN 104774287 A CN104774287 A CN 104774287A CN 201510108457 A CN201510108457 A CN 201510108457A CN 104774287 A CN104774287 A CN 104774287A
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 40
- 239000000839 emulsion Substances 0.000 title abstract description 25
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000178 monomer Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 17
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 23
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 20
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000006174 pH buffer Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 210000003608 fece Anatomy 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract 2
- 239000012875 nonionic emulsifier Substances 0.000 abstract 1
- 239000006179 pH buffering agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 21
- 238000000576 coating method Methods 0.000 description 18
- 238000004132 cross linking Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008094 contradictory effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
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- 239000000693 micelle Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a polyacrylate emulsion microgel, which is composed of the following raw materials in parts by weight: 2 to 2.4 parts of anionic emulsifier, 1.6 to 1.8 parts of nonionic emulsifier, 0.1 to 0.2 part of pH buffering agent, 1.5 to 3.3 parts of initiator, 25 to 35 parts of methyl methacrylate monomer, 65 to 75 parts of butyl acrylate monomer, 0.06 to 0.08 part of tert-butyl hydroperoxide, 0.06 to 0.08 part of rongalite, and 114.6 to 116.5 parts of deionized water. The microgel has the advantages of simple technology, compact and uniform film, and good waterproof property.
Description
(1) technical field
The present invention relates to polyacrylate dispersion microgel and preparation method thereof, be specifically related to a kind of polyacrylate dispersion microgel and preparation method thereof being applicable to water-borne coatings, ink system.
(2) background technology
Along with the enhancing day by day of people's environmental consciousness, high solids content and water-based system become one of the developing direction of coating, ink.High solids coatings, ink easily cause the rising of viscosity due to increase that solid divides, thus greatly affect construction usage effect.For solving " Gao Gu " and " low sticky " this contradiction, researcher takes many measures, wherein to be lowered into the molecular weight of film resin as major regulatory means (as introduced chain transfer agents in the process of letex polymerization synthetic resins, improve initiator concentration, improving temperature of reaction etc.).Although the decline of molecular resin amount can reduce the viscosity of system, improve its workability, the flowing down problems of coating, ink also occurs in the lump.Therefore this fails fundamentally to solve the contradiction of " Gao Gu " and " low sticky ".
Polymer microgel is one of new polymers of getting up of latest developments, is that one has colloid size (1 ~ 1000nm) and the polymer beads of intramolecular crosslinking.The preparation method of microgel has letex polymerization, solution polymerization, dispersed polymeres and precipitation polymerization etc.Due to emulsion polymerisation process energy-conserving and environment-protective, the microgel stable performance obtained, is therefore most widely used.Generally speaking, the viscosity of linear macromolecule and branched chain polymer solution is all very high, especially all the more so when high molecular.This is because random coil polymer molecular chain stretches to heavens in dilute solution, enhance the interaction between molecular chain and between molecular chain and solvent molecule.And polymer microgel exists compared with the crosslinking structure of the degree of depth because granule interior has, macromolecular chain is caused closely to be piled up, interaction between micro-gel particles and between micro-gel particles and dispersion medium is little, even if so under large arch dam (40 ~ 60%), the viscosity of system is also very low, especially all the more so when degree of crosslinking height.Therefore, polymer microgel be conducive to when keep low sticky improve the solid content of coating, ink.In water-borne coatings, ink system, polyacrylate type resin is the film-forming resin commonly used the most, is therefore applied to coating, the microgel of ink area focuses mostly on polyacrylate(s).The people such as Xu little Jun (Xu little Jun, Hu Jianhua, Yang Wuli, Deng. the preparation of Acrylate Microgel and sign [J] thereof. Fudan Journal (natural science edition), 1998,37 (3): 265-270) prepare the Acrylate Microgel of submicron order with dispersion copolymerization method, in coating, add the pseudo-plasticity that a small amount of microgel just significantly can improve coating.(poplar becomes the people such as Yang Cheng, Ma Zongbin, Luo Hui, Deng. the preparation of high concentration acrylic microgel dispersion and character [J]. chemical research and application, 2006,19 (7): 785-787) adopt microemulsion method to synthesize the polyacrylate(s) microgel of high density, and modification is carried out to high solids content Hydroxylated acrylic resin, make modified coating have obvious pseudo-plasticity.Zhou Xinhua (Zhou Xinhua. fabrication & properties research [D] of aqueous double-component acroleic acid polyurethane. Guangzhou: South China Science & Engineering University, 2005) a kind of hydroxyl acrylic emulsion with microgel nuclear structure has been synthesized, for the preparation of dual-component aqueous polyurethane, obtained aqueous polyurethane cross-linking density is high, and after being made into coating, anti-sag performance is good.But the complicated process of preparation of most of polyacrylate(s) microgel, and specific linking agent, polyfunctionality monomer (as dialkenyl monomers etc.) need be added or there is the cross-linking monomer of reactive group, this adds production cost undoubtedly.
N-butyl acrylate (BA, lower same) is one of emulsion polymerization conventional monomer preparing polyacrylate polymers, and the soft monomer of its Chang Zuowei telomerized polymer second-order transition temperature uses, and applies very extensive.The polymerization kinetics of BA under low temperature (-65 ~-7 DEG C) has obtained detailed research, but under the actual industrial production condition that temperature is relatively high the polymerization kinetics feature of (the common operation temperature as letex polymerization is 70 ~ 80 DEG C) recently studied scholar disclosed.1998, the people such as Lovell (Ahmad NM, Heatley F, Lovell PA.Chain transfer to polymer in free-radical solution polymerization ofn-butyl acrylate studied by NMR spectroscopy.Macromolecules 1998, 31:2822-2827) have studied the solution polymerization kinetics of BA at 70 DEG C, find that a rate of BA becomes positive correlation with the conversion rate of monomer, and when the initial monomer concentration of BA is greater than 10% (massfraction, lower same) time, free polymer readical easily forms branched structure by intermolecular chain tra nsfer, when the initial monomer concentration of BA is not more than 10%, free polymer readical easily forms branched structure by intramolecular chain tra nsfer.2000, the people such as Asua (Plesssis C, Arzamendi G, Leiza JR, Schoobrood HAS, Charmot D, AusaJM.A decrease in effective acylate propagation rate constants caused byintramolecular chain transfer.Macromolecules 2000, when 33:5041-5047) have studied 75 DEG C, the polymerization kinetics of BA under seed emulsion semi-continuous polymerzation operational condition is with its molecular chain structure, they pass through initiator concentration, the instantaneous conversion rate of the dripping quantity of monomer and time for adding regulation and control monomer, find that the percentage of grafting of BA raises with the rising of monomer instantaneous conversion rate, but its gel fraction does not but present obvious regularity.2007, the people such as Asua (Gonzalez I, Ausa JM, Leiza JR.The role of methyl methacrylateon branching and gel formation in the emulsion copolymerization of BA/MMA.Polymer 2007,48:2542-2547) have studied methyl methacrylate (MMA, lower with) with the emulsion copolymerization process of BA on a rate of polymkeric substance and the impact that formed in gel structure, find that the introducing of MMA can the part suppression branching reaction of BA and the formation of crosslinking structure.Above achievement in research enlightens us, in the acrylic ester monomer emulsion polymerization process based on BA, as long as by the regulation and control of different polymerization technique parameter, just likely control its branching reaction and crosslinking structure, thus without the need to add any additional cross-linking reagent, polyfunctionality monomer or there is reactive group the condition of cross-linking monomer under, prepare polyacrylate emulsion microgel.
The object of the invention is to overcome the deficiencies in the prior art, a kind of polyacrylate dispersion microgel not containing any additional cross-linking reagent or polyfunctionality monomer is provided.The maximum innovative point of the present invention is to utilize n-butyl acrylate that the feature of branching reaction easily occurs in emulsion polymerization process, adopt n-butyl acrylate the most common, methyl methacrylate is polymerization single polymerization monomer, when not introducing additional cross-linking reagent, polyfunctionality monomer and there is the cross-linking monomer of reactive group, by the control of polymerization technique, regulate a rate of BA and the formation of crosslinking structure, thus prepare polyacrylate emulsion microgel.On interior cross linked polyacrylate positive butyl ester microgel, introduce poly-(methyl methacrylate-co-n-butyl acrylate) thread-like molecule chain shell simultaneously, ensure the abundant diffusion of Microgels top layer polymer molecular chain in film process, make film forming more fine and close, even.This microgel water-resistance property of coating is good, is expected to be applied in water-borne coatings, ink system, solves the contradictory relation of its " Gao Gu " and " low sticky ", and promotes its pseudo-plasticity, improve workability.
(3) summary of the invention
The object of the present invention is to provide a kind of polyacrylate dispersion microgel and preparation method thereof, described polyacrylate dispersion microgel, adopt n-butyl acrylate the most common, methyl methacrylate is polymerization single polymerization monomer, just can form internally crosslinked latex particle system without the need to the cross-linking monomer introduced cross-linking reagent, polyfunctionality monomer or there is reactive group; On interior cross linked polyacrylate positive butyl ester microgel, introduce poly-(methyl methacrylate-co-n-butyl acrylate) thread-like molecule chain shell simultaneously, ensure the abundant diffusion of Microgels top layer polymer molecular chain in film process, make film forming more fine and close, even.This microgel water-resistance property of coating is good, is expected to be applied in water-borne coatings, ink system, solves the contradictory relation of its " Gao Gu " and " low sticky ", and promotes its pseudo-plasticity, improve workability.
The object of the invention is to be achieved through the following technical solutions:
A kind of polyacrylate dispersion microgel, described polyacrylate dispersion microgel is made up of the raw material of following weight proportion: anionic emulsifier 2 ~ 2.4 parts, nonionic emulsifying agent 1.6 ~ 1.8 parts, pH buffer reagent 0.1 ~ 0.2 part, initiator 1.5 ~ 3.3 parts, methyl methacrylate monomer 25 ~ 35 parts, n-butyl acrylate monomer 65 ~ 75 parts, tertbutyl peroxide 0.06 ~ 0.08 part, rongalite 0.06 ~ 0.08 part, deionized water 114.6 ~ 116.5 parts;
Further, described polyacrylate dispersion microgel obtains as follows:
(1) the pH buffer reagent of the nonionic emulsifying agent of the anionic emulsifier of 2 ~ 2.4 weight parts, 1.6 ~ 1.8 weight parts, 0.1 ~ 0.2 weight part, the n-butyl acrylate monomer of 5 weight parts are joined in the deionized water of 94.1 ~ 96 weight parts, stir under 300 ~ 700rpm condition and start to heat up, when temperature rises to 82 ~ 85 DEG C, velocity modulation to 150 ~ 250rpm will be stirred, add the initiator solution of 4.3 weight parts, this initiator solution is dissolved in the deionized water of 4 weight parts by the initiator of 0.3 weight part and obtains;
(2) after there is obvious blue light in question response system, the n-butyl acrylate monomer of 55 ~ 65 weight parts is dripped in 5 ~ 7 hours, the mixed solution of the n-butyl acrylate monomer of 5 weight parts and the methyl methacrylate monomer of 25 ~ 35 weight parts is dripped afterwards in 1 hour, and, while starting to drip monomer, drip the initiator solution of 13.7 ~ 15.5 weight parts, this initiator solution is dissolved in the deionized water of 12.5 weight parts by the initiator of 1.2 ~ 3 weight parts and obtains, and the time for adding of this initiator solution is 6.5 ~ 8.5 hours, control it to drip after complete 0.5 hour at all monomer droppings,
(3) reaction system insulated and stirred is after 1 hour, be cooled to 65 ~ 75 DEG C, add the tertbutyl peroxide aqueous solution, the described tertbutyl peroxide aqueous solution is dissolved in by the tertbutyl peroxide of 0.06 ~ 0.08 weight part in the deionized water of 2 weight parts and obtains, insulated and stirred 10 ~ 20 minutes, add the rongalite aqueous solution, the described rongalite aqueous solution is dissolved in by the rongalite of 0.06 ~ 0.08 weight part in the deionized water of 2 weight parts and obtains, insulated and stirred 10 ~ 20 minutes, finally be down to room temperature discharging, obtain described polyacrylate dispersion microgel;
Wherein, described anionic emulsifier is selected from the mixture of any one or two or more arbitrary proportion in PS-625A (Shanghai loyal Fine Chemical Co., Ltd), PS-625S (the loyal Fine Chemical Co., Ltd in Shanghai), PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai), PS-725S (the loyal Fine Chemical Co., Ltd in Shanghai), PS-925 (the loyal Fine Chemical Co., Ltd in Shanghai);
Described nonionic emulsifying agent is selected from
s70 (SASOL),
s90 (SASOL),
the mixture of any one or two or more arbitrary proportion in LE407k (SASOL);
Described pH buffer reagent be selected from sodium bicarbonate, sodium carbonate, AMP-95 (Dow company) any one;
Described initiator be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate any one.
Polyacrylate dispersion microgel of the present invention, preferably described anionic emulsifier is PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai).
Preferably described nonionic emulsifying agent is
lE407k (SASOL).
Preferably described pH buffer reagent is sodium bicarbonate.
Preferably described initiator is Sodium Persulfate.
Polyacrylate dispersion microgel of the present invention, is particularly preferably made up of the raw material of following weight proportion: anionic emulsifier PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai) 2 ~ 2.4 parts, nonionic emulsifying agent
lE407k (SASOL) 1.6 ~ 1.8 parts, pH buffer reagent sodium bicarbonate 0.1 ~ 0.2 part, initiator Sodium Persulfate 1.5 ~ 3.3 parts, methyl methacrylate monomer 28 ~ 32 parts, n-butyl acrylate monomer 68 ~ 72 parts, tertbutyl peroxide 0.06 ~ 0.08 part, rongalite 0.06 ~ 0.08 part, deionized water 114.6 ~ 116.5 parts.
The present invention utilizes n-butyl acrylate that the feature of branching reaction easily occurs in emulsion polymerization process, when not introducing additional cross-linking reagent and polyfunctionality monomer, by suitably improving the strategies such as temperature of reaction (82 ~ 85 DEG C), the dropping of high density initiator and the slow dropping of monomer, improve the instantaneous conversion rate of monomer, thus improve the instantaneous ratio of free polymer readical and monomer, promote the generation of polymer molecule interchain chain tra nsfer, thus form the microgel emulsion with long chain branch, interior crosslinking structure.The process of emulsion particle film forming comprises the volatilization of moisture, the gathering of emulsion particle, ordered arrangement, coalescence, distortion, and the stage such as diffusion, winding of emulsion particle distortion post-consumer polymer molecular chain-end.For the emulsion particle with crosslinking structure, film forming properties will be subject to the diffusion of film process Middle molecule chain and crosslinked extreme influence.If molecular chain entirety is crosslinked fine and close in emulsion particle, easily cause in film process, the diffusion of molecular chain is subject to the suppression of crosslinking structure thus affects film performance.And the present invention introduces poly-(methyl methacrylate-co-n-butyl acrylate) shell on interior cross linked polyacrylate positive butyl ester microgel, the introducing of methyl methacrylate not only increases the second-order transition temperature of latex particle, is more conducive to forming non-branching, crosslinked shell structure.Shell linear structure can ensure the abundant diffusion of Microgels top layer polymer molecular chain in film process, makes film forming more fine and close, even.
Compared with prior art, the present invention has following advantage:
1, utilize n-butyl acrylate that the feature of branching reaction easily occurs in emulsion polymerization process, adopt n-butyl acrylate the most common, methyl methacrylate is polymerization single polymerization monomer, by simple technology controlling and process, when not introducing additional cross-linking reagent and polyfunctionality monomer, the preparation of polyacrylate dispersion microgel can be realized;
2, on interior cross linked polyacrylate positive butyl ester microgel, introduce poly-(methyl methacrylate-co-n-butyl acrylate) thread-like molecule chain shell, ensure the abundant diffusion of Microgels top layer polymer molecular chain in film process, make film forming more fine and close, even;
The Microgels 3, with interior crosslinking structure enhances the water resistance of film.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
In embodiment, solid content refers to emulsion per-cent of quality of the emulsion before residuum quality and drying after 100 DEG C of forced air drying 24h;
In emulsion, the particle diameter test of latex particle is carried out on Malvern ZETASIZER 3000HAS particle size analyzer, and probe temperature is 25 DEG C;
The package stability of emulsion refers to that ink leaves standstill 9 days under 60 DEG C of conditions, not precipitate, not stratifiedly represents emulsion package stability >6 month;
The test of emulsion gel content refers to and emulsion is coated with forced air drying 24h at 100 DEG C on a glass, after take the microgel dry film of certain mass, wrap with filter paper and fasten rear weighing with copper wire, put into apparatus,Soxhlet's, with acetone reflux extracting 48h, 100 DEG C of air blast are dried to constant weight, weigh, quality change percentage ratio before and after the extracting of microgel film is gel content, with its measuring as crosslinking degree;
Emulsion microgel water-resistance property of coating measures by the measuring method of GB/T 1733-1993.
Embodiment 1
(1) by 2.2g PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai), 1.8g
lE407k (SASOL company), 0.1g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer join in 96g deionized water, stir and start to heat up under 300rpm condition; When temperature rises to 85 DEG C, stirring is adjusted to 150rpm, adds 4.3g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (0.3g Sodium Persulfate is dissolved in 4g deionized water);
(2) after there is obvious blue light in question response system, 58g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped in 7 hours, the mixed solution of 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer and 32g methyl methacrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped afterwards in 1 hour, and, while starting to drip monomer, drip 13.7g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (1.2g Sodium Persulfate is dissolved in 12.5g deionized water), and the time for adding of sodium persulfate aqueous solution is 8.5 hours, control it to drip after complete 0.5 hour at all monomer droppings,
(3) reaction system insulated and stirred was cooled to 75 DEG C after 1 hour, add tertbutyl peroxide (the Shanghai 101 Chemical Co., Ltd.) aqueous solution (0.06g tertbutyl peroxide is dissolved in 2g deionized water), insulated and stirred 15 minutes, add rongalite (the auspicious Chemical Co., Ltd. of the Shanghai Feng) aqueous solution (0.06g rongalite is dissolved in 2g deionized water), insulated and stirred 15 minutes; After be cooled to room temperature discharging, polyacrylate dispersion microgel can be obtained.
Embodiment 2
(1) by 2g PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai), 1.8g
lE407k (SASOL company), 0.12g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer join in 95.34g deionized water, stir and start to heat up under 700rpm condition; When temperature rises to 82 DEG C, stirring is adjusted to 200rpm, adds 4.3g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (0.3g Sodium Persulfate is dissolved in 4g deionized water);
(2) after there is obvious blue light in question response system, 60g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped in 6 hours, the mixed solution of 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer and 30g methyl methacrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped afterwards in 1 hour, and, while starting to drip monomer, drip 14.5g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (2g Sodium Persulfate is dissolved in 12.5g deionized water), and the time for adding of sodium persulfate aqueous solution is 7.5 hours, control it to drip after complete 0.5 hour at all monomer droppings,
(3) reaction system insulated and stirred was cooled to 65 DEG C after 1 hour, add tertbutyl peroxide (the Shanghai 101 Chemical Co., Ltd.) aqueous solution (0.08g tertbutyl peroxide is dissolved in 2g deionized water), insulated and stirred 20 minutes, add rongalite (the auspicious Chemical Co., Ltd. of the Shanghai Feng) aqueous solution (0.08g rongalite is dissolved in 2g deionized water), insulated and stirred 20 minutes; After be cooled to room temperature discharging, polyacrylate dispersion microgel can be obtained.
Embodiment 3
(1) by 2.4g PS-725A (the loyal Fine Chemical Co., Ltd in Shanghai), 1.6g
lE407k (SASOL company), 0.2g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer join in 94.1g deionized water, stir and start to heat up under 550rpm condition; When temperature rises to 83 DEG C, stirring is adjusted to 250rpm, adds 4.3g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (0.3g Sodium Persulfate is dissolved in 4g deionized water);
(2) occur after obvious blue light until system, 62g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped in 5 hours, the mixed solution of 5g n-butyl acrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer and 28g methyl methacrylate (Guangzhou Zhong Ye Chemical Co., Ltd.) monomer is dripped afterwards in 1 hour, and, while starting to drip monomer, drip 15.5g Sodium Persulfate (Suzhou Chemical Industry Science Co., Ltd of the China Airlines Limited) aqueous solution (3g Sodium Persulfate is dissolved in 12.5g deionized water), and the time for adding of sodium persulfate aqueous solution is 6.5 hours, control it to drip after complete 0.5 hour at all monomer droppings,
(3) reaction system insulated and stirred was cooled to 70 DEG C after 1 hour, add tertbutyl peroxide (the Shanghai 101 Chemical Co., Ltd.) aqueous solution (0.06g tertbutyl peroxide is dissolved in 2g deionized water), insulated and stirred 10 minutes, add rongalite (the auspicious Chemical Co., Ltd. of the Shanghai Feng) aqueous solution (0.06g rongalite is dissolved in 2g deionized water), insulated and stirred 10 minutes; After be cooled to room temperature discharging, polyacrylate dispersion microgel can be obtained.
Table 1. polyacrylate dispersion microgel performance
As shown in Table 1, the polyacrylate dispersion microgel particle diameter prepared of the inventive method is less; Stability of emulsion is better, and package stability has all exceeded 6 months, can meet and produce storage request normally; Gel content, more than 70%, demonstrates the crosslinking structure of micelle inside on the one hand, also demonstrates the linear molecule chain structure that micelle inside exists on the other hand; Even, fine and close after emulsion microgel film forming, there is not unsound phenomenon after common microgel film forming, in addition water-resistance property of coating is splendid, soak in water after 48 hours, film coated surface is non-foaming, film does not come off, and its good film forming properties and water resistance demonstrate " interior crosslinked core-outside line shell " structure of patent microgel uniqueness of the present invention.This polyacrylate dispersion microgel is expected to be applied in water-borne coatings, ink system, solves the contradictory relation of its " Gao Gu " and " low sticky ", and promotes its pseudo-plasticity energy.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (5)
1. a polyacrylate dispersion microgel, it is characterized in that, described polyacrylate dispersion microgel is made up of the raw material of following weight proportion: anionic emulsifier 2 ~ 2.4 parts, nonionic emulsifying agent 1.6 ~ 1.8 parts, pH buffer reagent 0.1 ~ 0.2 part, initiator 1.5 ~ 3.3 parts, methyl methacrylate monomer 25 ~ 35 parts, n-butyl acrylate monomer 65 ~ 75 parts, tertbutyl peroxide 0.06 ~ 0.08 part, rongalite 0.06 ~ 0.08 part, deionized water 114.6 ~ 116.5 parts;
Further, described polyacrylate dispersion microgel obtains as follows:
(1) the pH buffer reagent of the nonionic emulsifying agent of the anionic emulsifier of 2 ~ 2.4 weight parts, 1.6 ~ 1.8 weight parts, 0.1 ~ 0.2 weight part, the n-butyl acrylate monomer of 5 weight parts are joined in the deionized water of 94.1 ~ 96 weight parts, stir under 300 ~ 700rpm condition and start to heat up, when temperature rises to 82 ~ 85 DEG C, velocity modulation to 150 ~ 250rpm will be stirred, add the initiator solution of 4.3 weight parts, this initiator solution is dissolved in the deionized water of 4 weight parts by the initiator of 0.3 weight part and obtains;
(2) after there is obvious blue light in question response system, the n-butyl acrylate monomer of 55 ~ 65 weight parts is dripped in 5 ~ 7 hours, the mixed solution of the n-butyl acrylate monomer of 5 weight parts and the methyl methacrylate monomer of 25 ~ 35 weight parts is dripped afterwards in 1 hour, and, while starting to drip monomer, drip the initiator solution of 13.7 ~ 15.5 weight parts, this initiator solution is dissolved in the deionized water of 12.5 weight parts by the initiator of 1.2 ~ 3 weight parts and obtains, and the time for adding of this initiator solution is 6.5 ~ 8.5 hours, control it to drip after complete 0.5 hour at all monomer droppings,
(3) reaction system insulated and stirred is after 1 hour, be cooled to 65 ~ 75 DEG C, add the tertbutyl peroxide aqueous solution, the described tertbutyl peroxide aqueous solution is dissolved in by the tertbutyl peroxide of 0.06 ~ 0.08 weight part in the deionized water of 2 weight parts and obtains, insulated and stirred 10 ~ 20 minutes, add the rongalite aqueous solution, the described rongalite aqueous solution is dissolved in by the rongalite of 0.06 ~ 0.08 weight part in the deionized water of 2 weight parts and obtains, insulated and stirred 10 ~ 20 minutes, finally be down to room temperature discharging, obtain described polyacrylate dispersion microgel;
Wherein, described anionic emulsifier is selected from the mixture of any one or two or more arbitrary proportion in PS-625A, PS-625S, PS-725A, PS-725S, PS-925;
Described nonionic emulsifying agent is selected from the production of SASOL company
s70,
s90,
the mixture of any one or two or more arbitrary proportion in LE407k;
Described pH buffer reagent be selected from sodium bicarbonate, sodium carbonate, AMP-95 any one;
Described initiator be selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate any one.
2. polyacrylate dispersion microgel as claimed in claim 1, it is characterized in that, described anionic emulsifier is PS-725A.
3. polyacrylate dispersion microgel as claimed in claim 1, is characterized in that, described nonionic emulsifying agent is that SASOL company produces
lE407k.
4. polyacrylate dispersion microgel as claimed in claim 1, it is characterized in that, described pH buffer reagent is sodium bicarbonate.
5. polyacrylate dispersion microgel as claimed in claim 1, it is characterized in that, described initiator is Sodium Persulfate.
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| CN110918068A (en) * | 2019-12-12 | 2020-03-27 | 西安工业大学 | Nano zero-valent iron microgel composite material and preparation method and regeneration method thereof |
| CN110918068B (en) * | 2019-12-12 | 2022-12-20 | 西安工业大学 | Nano zero-valent iron microgel composite material and preparation method and regeneration method thereof |
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Application publication date: 20150715 Assignee: Lishui Hewitt New Material Co.,Ltd. Assignor: HANGZHOU HIWETECH CHEMICAL TECHNOLOGY Co.,Ltd. Contract record no.: X2023330000866 Denomination of invention: Polyacrylate lotion micro gel and its preparation method Granted publication date: 20170426 License type: Common License Record date: 20231120 |