CN104774287B - Polyacrylate emulsion microgel and preparation method thereof - Google Patents
Polyacrylate emulsion microgel and preparation method thereof Download PDFInfo
- Publication number
- CN104774287B CN104774287B CN201510108457.9A CN201510108457A CN104774287B CN 104774287 B CN104774287 B CN 104774287B CN 201510108457 A CN201510108457 A CN 201510108457A CN 104774287 B CN104774287 B CN 104774287B
- Authority
- CN
- China
- Prior art keywords
- monomer
- weight portions
- microgel
- parts
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 39
- 239000000839 emulsion Substances 0.000 title abstract description 26
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000178 monomer Substances 0.000 claims abstract description 56
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000012875 nonionic 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 28
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000006174 pH buffer Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 210000003608 fece Anatomy 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- -1 Butyl peroxy Chemical group 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 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
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 101710171243 Peroxidase 10 Proteins 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000012874 anionic emulsifier Substances 0.000 abstract 1
- 239000006179 pH buffering agent Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 239000003643 water by type Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 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 description 3
- 229910000004 White lead Inorganic materials 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
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 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
- 102400000830 Saposin-B Human genes 0.000 description 1
- 101800001697 Saposin-B Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 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
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- 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, and in particular to one kind is applicable to aqueouss painting
Material, polyacrylate dispersion microgel of ink system and preparation method thereof.
(2) background technology
With the increasingly enhancing of people's environmental consciousness, high solids content and water-based system become the developing direction of coating, ink
One of.High solids coatings, ink easily cause the rising of viscosity due to the increase of solid point, so as to greatly affect construction to make
Use effect.To solve " Gao Gu " and " low viscous " this contradiction, researcher takes many measures, wherein to reduce film-forming resin
Molecular weight as major regulatory means (such as during emulsion polymerization synthetic resin introduce chain transfer agents, improve cause
Agent concentration, raising reaction temperature etc.).Although the decline of molecular resin amount can reduce the viscosity of system, its workability is improved,
But the flowing down problems of coating, ink also occur in the lump.Therefore this fails the contradiction for fundamentally solving " Gao Gu " and " low viscous ".
Polymer microgel is one of new polymerss that latest developments are got up, be it is a kind of have colloid size (1~
1000nm) and intramolecular crosslinking polymer beads.The preparation method of microgel has emulsion polymerization, polymerisation in solution, dispersin polymerization
Thing and precipitation polymerization etc..Due to emulsion polymerisation process energy-conserving and environment-protective, the microgel stable performance for obtaining, therefore application is the widest
It is general.In general, the viscosity of linear macromolecule and branch polymer solution is very high, especially it is even more such as in high molecular
This.This is because random coil polymer molecular chain highly stretches in weak solution, molecule interchain and strand are enhanced
Interaction between solvent molecule.And polymer microgel is due to the presence of the cross-linked structure compared with depth, causing inside granule
Macromolecular chain is closely piled up, and the interaction between micro-gel particles and between micro-gel particles and disperse medium is little, so
Even if under large arch dam (40~60%), the viscosity of system is also very low, especially even more so when the degree of cross linking is high.Therefore, gather
Compound microgel is conducive to the solid content that coating, ink are improved in the case where low gluing is kept.In water paint, ink system
In, polyacrylate type resin is the most commonly used film-forming resin, therefore be applied to coating, the microgel of ink area focuses mostly on
On polyacrylate.Xu little Jun et al. (Xu little Jun, Hu Jianhua, Yang Wuli, etc. Acrylate Microgel preparation and
Which characterizes [J]. Fudan Journal (natural science edition), 1998,37 (3):Submicron order is prepared with dispersion copolymerization method 265-270)
Acrylate Microgel, add the pseudoplastic behavior that a small amount of microgel can just significantly improve coating in coating.Yang Cheng etc.
People (poplar into, Ma Zongbin, Luo Hui, etc. the preparation of high concentration acrylic microgel dispersion and property [J]. chemical research with
Using 2006,19 (7):785-787) synthesize the polyacrylate microgel of high concentration using microemulsion method, and to Gao Gu
Content Hydroxylated acrylic resin is modified, and makes modified coating have obvious pseudoplastic behavior.Zhou Xinhua (Zhou Xinhua. aqueouss
The preparation of double-component acrylic acid polyurethane and performance study [D]. Guangzhou:South China Science & Engineering University, 2005) has synthesized a kind of with micro-
The hydroxyl acrylic emulsion of gel nuclear structure, for preparing dual-component aqueous polyurethane, obtained aqueous polyurethane crosslink density
Height, after being made into coating, sag resistance can be good.But the complicated process of preparation of most of polyacrylate microgel, and need addition
Specific cross-linking agent, polyfunctional monomer (such as dialkenyl monomers etc.) or the cross-linking monomer with reactive group, this undoubtedly increases
Production cost is added.
N-butyl acrylate (BA, similarly hereinafter) be emulsion polymerization prepare polyacrylate polymers conventional monomer it
One, which is used frequently as the soft monomer for adjusting polymer glass temperature, using quite varied.BA is at low temperature (- 65~-7 DEG C)
Under kinetics of polymerization studied in detail, but (such as emulsion under the conditions of the of a relatively high actual industrial production of temperature
The common operation temperature of polymerization is 70~80 DEG C) kinetics of polymerization feature recently disclosed in studied scholar.1998
Year, Lovell et al. (Ahmad NM, Heatley F, Lovell PA.Chain transfer to polymer in free-
radical solution polymerization of n-butyl acrylate studied by NMR
spectroscopy.Macromolecules 1998,31:Polymerisation in solution power of the BA at 70 DEG C is have studied 2822-2827)
Learn, the conversion rate of a rate and monomer of BA is found into positive correlation, and when the initial monomer concentration of BA is more than 10% (matter
Amount fraction, similarly hereinafter) when, free polymer readical forms branched structure easily by intermolecular chain tra nsfer;When the initial monomer of BA
When concentration is not more than 10%, free polymer readical forms branched structure easily by intramolecular chain tra nsfer.2000, Asua etc.
People (Plesssis C, Arzamendi G, Leiza JR, Schoobrood HAS, Charmot D, Ausa JM.A
decrease in effective acylate propagation rate constants caused by
intramolecular chain transfer.Macromolecules 2000,33:When 5041-5047) have studied 75 DEG C,
, with its molecular chain structure, they are dense by initiator for kinetics of polymerizations of the BA under seed emulsion semi-continuous polymerization operating condition
Degree, the dripping quantity of monomer and time for adding regulate and control the instantaneous conversion rate of monomer, find the percent grafting of BA with monomer instantaneous conversion rate
Rising and raise, but its gel fraction is but presented significantly regular.2007, Asua et al. (Gonzalez I,
Ausa JM,Leiza JR.The role of methyl methacrylate on branching and gel
formation in the emulsion copolymerization of BA/MMA.Polymer 2007,48:2542-
2547) rate and shape of the methyl methacrylate (MMA, similarly hereinafter) to polymer during the emulsion copolymerization with BA be have studied
Into the impact in terms of gel structure, it is found that the introducing of MMA can partly suppress the formation of the branching reaction and cross-linked structure of BA.With
Upper achievement in research enlightens us, in the acrylic ester monomer emulsion polymerization process based on BA, as long as by different poly-
Close the regulation and control of technological parameter, it is possible to control its branching reaction and cross-linked structure, so as to any additional crosslinking need not be being added
Under conditions of reagent, polyfunctional monomer or the cross-linking monomer with reactive group, polyacrylate emulsion is prepared micro-
Gel.
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of not contain any additional cross-linking reagent or multifunctional
The polyacrylate dispersion microgel of degree monomer.Maximum innovative point of the invention is in emulsion polymerization using n-butyl acrylate
During the characteristics of easily there is branching reaction, adopt most commonly seen n-butyl acrylate, methyl methacrylate for polymerization singly
Body, in the case where additional cross-linking reagent, polyfunctional monomer and the cross-linking monomer with reactive group is not introduced, by poly-
The control of technique is closed, a rate and the formation of cross-linked structure of BA is adjusted, so as to prepare polyacrylate emulsion microgel.
Poly- (methyl methacrylate-co- n-butyl acrylates) line is introduced on interior cross linked polyacrylate N-butyl microgel simultaneously
Type strand shell, it is ensured that the abundant diffusion of Microgels top layer polymer molecular chain in film forming procedure, makes film forming more cause
It is close, uniform.This microgel water-resistance property of coating is good, is expected to be applied in water paint, ink system, solves which " Gao Gu " and " low
It is viscous " contradictory relation, and lift its pseudoplastic behavior, improve workability.
(3) content of the invention
It is an object of the invention to provide a kind of polyacrylate dispersion microgel and preparation method thereof, the polyacrylic acid
Ester emulsion microgel, adopts most commonly seen n-butyl acrylate, methyl methacrylate for polymerized monomer, without the need for introducing crosslinked
Reagent, polyfunctional monomer or the cross-linking monomer with reactive group can just form internally crosslinked latex particle system;Together
When poly- (methyl methacrylate-co- n-butyl acrylates) line style is introduced on interior cross linked polyacrylate N-butyl microgel
Strand shell, it is ensured that the abundant diffusion of Microgels top layer polymer molecular chain in film forming procedure, make film forming it is more fine and close,
Uniformly.This microgel water-resistance property of coating is good, is expected to be applied in water paint, ink system, solves its " Gao Gu " and " low viscous "
Contradictory relation, and lift its pseudoplastic behavior, improve workability.
The purpose of the present invention is achieved through the following technical solutions:
A kind of polyacrylate dispersion microgel, raw material of the polyacrylate dispersion microgel by following weight proportion
Composition:2~2.4 parts of anion emulsifier, 1.6~1.8 parts of nonionic emulsifier, 0.1~0.2 part of pH buffer, initiator 1.5
~3.3 parts, 25~35 parts of methyl methacrylate monomer, 65~75 parts of n-butyl acrylate monomer, tert-butyl hydroperoxide
0.06~0.08 part, 0.06~0.08 part of rongalite, 114.6~116.5 parts of deionized water;
Also, the polyacrylate dispersion microgel is obtained as follows:
(1) by the anion emulsifier of 2~2.4 weight portions, the nonionic emulsifier of 1.6~1.8 weight portions, 0.1~0.2
The pH buffer of weight portion, the n-butyl acrylate monomer of 5 weight portions are added in the deionized water of 94.1~96 weight portions,
Stir under the conditions of 300~700rpm and start to warm up, when temperature rises to 82~85 DEG C, velocity modulation will be stirred to 150~250rpm, plus
Enter the initiator solution of 4.3 weight portions, the initiator solution is dissolved in going for 4 weight portions by the initiator of 0.3 weight portion
Obtain in ionized water;
(2), after obvious blue light occurs in question response system, the acrylic acid for dripping 55~65 weight portions in 5~7 hours is just
Butyl ester monomer, dripped the metering system of the n-butyl acrylate monomer and 25~35 weight portions of 5 weight portions afterwards in 1 hour
The mixed liquor of sour methylmethacrylate monomer, also, while Deca monomer is started, the initiator of 13.7~15.5 weight portion of Deca is water-soluble
Liquid, the initiator solution are dissolved in the deionized water of 12.5 weight portions by the initiator of 1.2~3 weight portions and are obtained, and
The time for adding of the initiator solution is 6.5~8.5 hours, controls its Deca after complete 0.5 hour of all monomer droppings
It is complete;
(3) reaction system insulated and stirred was cooled to 65~75 DEG C after 1 hour, added tert-butyl hydroperoxide aqueous solution, institute
State the deionization that tert-butyl hydroperoxide aqueous solution is dissolved in 2 weight portions by the tert-butyl hydroperoxide of 0.06~0.08 weight portion
Obtain in water, insulated and stirred 10~20 minutes, add rongalite aqueous solution, the rongalite aqueous solution is by 0.06~0.08 weight
The rongalite of part is obtained in being dissolved in the deionized water of 2 weight portions, insulated and stirred 10~20 minutes, is finally down to room temperature discharging,
Obtain final product described polyacrylate dispersion microgel;
Wherein, the anion emulsifier selected from PS-625A (Shanghai loyalty Fine Chemical Co., Ltd), PS-625S (on
Extra large loyalty Fine Chemical Co., Ltd), PS-725A (Shanghai loyalty Fine Chemical Co., Ltd), PS-725S (the loyal essences in Shanghai
Thin Chemical Co., Ltd.), any one or two or more any ratios in PS-925 (Shanghai loyalty Fine Chemical Co., Ltd)
The mixture of example;
The nonionic emulsifier is selected fromS70(SASOL)、S90
(SASOL)、The mixture of any one or two or more arbitrary proportions in LE407k (SASOL);
The pH buffer is selected from any one in sodium bicarbonate, sodium carbonate, AMP-95 (Dow companies);
The initiator is selected from any one in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
Polyacrylate dispersion microgel of the present invention, preferably described anion emulsifier are PS-725A (the loyal essences in Shanghai
Thin Chemical Co., Ltd.).
It is preferred that described nonionic emulsifier isLE407k(SASOL)。
It is preferred that described pH buffer is sodium bicarbonate.
It is preferred that described initiator is sodium peroxydisulfate.
Polyacrylate dispersion microgel of the present invention, is particularly preferably made up of the raw material of following weight proportion:It is cloudy
2~2.4 parts of ionic emulsifying agent PS-725A (Shanghai loyalty Fine Chemical Co., Ltd), nonionic emulsifier1.6~1.8 parts of LE407k (SASOL), 0.1~0.2 part of pH buffer sodium bicarbonate, initiator over cure
1.5~3.3 parts of sour sodium, 28~32 parts of methyl methacrylate monomer, 68~72 parts of n-butyl acrylate monomer, t-butyl peroxy
Change 0.06~0.08 part of hydrogen, 0.06~0.08 part of rongalite, 114.6~116.5 parts of deionized water.
The characteristics of easily there is branching reaction using n-butyl acrylate in emulsion polymerization process in the present invention, it is outer not introducing
Plus in the case of cross-linking reagent and polyfunctional monomer, by properly increasing reaction temperature (82~85 DEG C), high concentration initiator
Deca and monomer the instantaneous conversion rate for the strategy such as being slowly added dropwise, improving monomer, so as to improve free polymer readical and list
The instantaneous ratio of body, promotes the generation of polymer molecule interchain chain tra nsfer, so as to be formed with long chain branch, interior cross-linked structure
Microgel emulsion.The process of emulsion particle film forming includes the volatilization of moisture, the aggregation of emulsion particle, ordered arrangement, coalescence, deformation,
And emulsion particle deforms the stages such as the diffusion of post-consumer polymer molecular chain-end, winding.For the emulsion particle with cross-linked structure,
Filming performance is by by strand diffusion in film forming procedure and the extreme influence being crosslinked.If latex intragranular strand is integrally crosslinked cause
It is close, it is easily caused in film forming procedure, the diffusion of strand is suppressed so as to affect film performance by cross-linked structure.And this
It is bright that poly- (methyl methacrylate-co- n-butyl acrylates) shell is introduced on interior cross linked polyacrylate N-butyl microgel,
The introducing of methyl methacrylate not only increases the vitrification point of latex particle, is more beneficial for being formed non-branching, crosslinking
Shell structurre.Shell linear structure can ensure that the abundant diffusion of Microgels top layer polymer molecular chain in film forming procedure,
Make film forming more fine and close, uniform.
Compared with prior art, the present invention has following advantage:
1st, the characteristics of easily there is branching reaction using n-butyl acrylate in emulsion polymerization process, using most commonly seen
N-butyl acrylate, methyl methacrylate are polymerized monomer, by simple technology controlling and process, are not introducing additional cross-linking reagent
In the case of polyfunctional monomer, you can realize the preparation of polyacrylate dispersion microgel;
2nd, poly- (the positive fourth of methyl methacrylate-co- acrylic acid is introduced on interior cross linked polyacrylate N-butyl microgel
Ester) linear molecule chain shell, it is ensured that the abundant diffusion of Microgels top layer polymer molecular chain in film forming procedure, make film forming more
For densification, uniformly;
3rd, the Microgels with interior cross-linked structure enhance the water resistance of film.
(4) specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
In embodiment solid content refer to emulsion after 100 DEG C of forced air drying 24h residue quality be dried before quality of the emulsion
Percentage ratio;
The particle diameter test of latex particle in emulsion is carried out on Malvern ZETASIZER 3000HAS particle size analyzers, is tested
Temperature is 25 DEG C;
The bin stability of emulsion refers to that ink stands 9 days under the conditions of 60 DEG C, not precipitate, it is not stratified represent emulsion storage
Deposit stability>6 months;
The test of emulsion gel content refers to and for emulsion to apply the forced air drying 24h at 100 DEG C on a glass, after weigh one
Determine the microgel dry film of quality, wrapped with filter paper and weighed after being fastened with copper wire, be put into apparatus,Soxhlet'ses, extracted with acetone reflux
48h, 100 DEG C of air blast are dried to constant weight, are weighed, and the mass change percent before and after the extracting of microgel film is gel content,
With its measuring as crosslinking degree;
Emulsion microgel water-resistance property of coating is measured by the assay method of GB/T 1733-1993.
Embodiment 1
(1) by 2.2g PS-725A (Shanghai loyalty Fine Chemical Co., Ltd), 1.8gLE407k
(SASOL companies), 0.1g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylates (industry in Guangzhou
Chemical Co., Ltd.) monomer is added in 96g deionized waters, stirs and start to warm up under the conditions of 300rpm;When temperature rises to 85
DEG C when, stirring is adjusted to into 150rpm, 4.3g sodium peroxydisulfates (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited) aqueous solution (0.3g mistakes are added
Sodium sulfate is dissolved in 4g deionized waters);
(2), after obvious blue light occurs in question response system, 58g n-butyl acrylates (industry in Guangzhou is dripped in 7 hours
Chemical Co., Ltd.) monomer, 5g n-butyl acrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) were dripped singly in 1 hour afterwards
The mixed liquor of body and 32g methyl methacrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) monomer, also, starting Deca monomer
While, (1.2g sodium peroxydisulfates are dissolved in aqueous solution Deca 13.7g sodium peroxydisulfate (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited)
In 12.5g deionized waters), and the time for adding of sodium persulfate aqueous solution is 8.5 hours, controls which complete in all monomer droppings
Drip after 0.5 hour;
(3) reaction system insulated and stirred is cooled to 75 DEG C after 1 hour, adds tert-butyl hydroperoxide (101 chemical industry of Shanghai
Company limited) aqueous solution (0.06g tert-butyl hydroperoxide is dissolved in 2g deionized waters), insulated and stirred 15 minutes, addition carving
White lead (the auspicious Chemical Co., Ltd.s of Shanghai Feng) aqueous solution (0.06g rongalite is dissolved in 2g deionized waters), 15 points of insulated and stirred
Clock;After be cooled to room temperature discharging, you can obtain polyacrylate dispersion microgel.
Embodiment 2
(1) by 2g PS-725A (Shanghai loyalty Fine Chemical Co., Ltd), 1.8gLE407k
(SASOL companies), 0.12g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylates (industry in Guangzhou
Chemical Co., Ltd.) monomer is added in 95.34g deionized waters, stirs and start to warm up under the conditions of 700rpm;When temperature rises to
When 82 DEG C, stirring is adjusted to into 200rpm, adds 4.3g sodium peroxydisulfates (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited) aqueous solution (0.3g
Sodium peroxydisulfate is dissolved in 4g deionized waters);
(2), after obvious blue light occurs in question response system, 60g n-butyl acrylates (industry in Guangzhou is dripped in 6 hours
Chemical Co., Ltd.) monomer, 5g n-butyl acrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) were dripped singly in 1 hour afterwards
The mixed liquor of body and 30g methyl methacrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) monomer, also, starting Deca monomer
While, (2g sodium peroxydisulfates are dissolved in aqueous solution Deca 14.5g sodium peroxydisulfate (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited)
In 12.5g deionized waters), and the time for adding of sodium persulfate aqueous solution is 7.5 hours, controls which complete in all monomer droppings
Drip after 0.5 hour;
(3) reaction system insulated and stirred is cooled to 65 DEG C after 1 hour, adds tert-butyl hydroperoxide (101 chemical industry of Shanghai
Company limited) aqueous solution (0.08g tert-butyl hydroperoxide is dissolved in 2g deionized waters), insulated and stirred 20 minutes, addition carving
White lead (the auspicious Chemical Co., Ltd.s of Shanghai Feng) aqueous solution (0.08g rongalite is dissolved in 2g deionized waters), 20 points of insulated and stirred
Clock;After be cooled to room temperature discharging, you can obtain polyacrylate dispersion microgel.
Embodiment 3
(1) by 2.4g PS-725A (Shanghai loyalty Fine Chemical Co., Ltd), 1.6gLE407k
(SASOL companies), 0.2g sodium bicarbonate (Shanghai Ai Bi chemical reagent company limited), 5g n-butyl acrylates (industry in Guangzhou
Chemical Co., Ltd.) monomer is added in 94.1g deionized waters, stirs and start to warm up under the conditions of 550rpm;When temperature rises to
When 83 DEG C, stirring is adjusted to into 250rpm, adds 4.3g sodium peroxydisulfates (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited) aqueous solution (0.3g
Sodium peroxydisulfate is dissolved in 4g deionized waters);
(2) after obvious blue light occurs in system, 62g n-butyl acrylates (industry chemical industry in Guangzhou is dripped in 5 hours
Company limited) monomer, dripped in 1 hour afterwards 5g n-butyl acrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) monomer with
The mixed liquor of 28g methyl methacrylates (Guangzhou Zhong Ye Chemical Co., Ltd.s) monomer, also, starting the same of Deca monomer
When, (3g sodium peroxydisulfates are dissolved in 12.5g and go aqueous solution Deca 15.5g sodium peroxydisulfate (Suzhou Chemical Industry Science Co., Ltd of China Airlines Limited)
In ionized water), and the time for adding of sodium persulfate aqueous solution is 6.5 hours, controls which complete 0.5 hour in all monomer droppings
After drip;
(3) reaction system insulated and stirred is cooled to 70 DEG C after 1 hour, adds tert-butyl hydroperoxide (101 chemical industry of Shanghai
Company limited) aqueous solution (0.06g tert-butyl hydroperoxide is dissolved in 2g deionized waters), insulated and stirred 10 minutes, addition carving
White lead (the auspicious Chemical Co., Ltd.s of Shanghai Feng) aqueous solution (0.06g rongalite is dissolved in 2g deionized waters), 10 points of insulated and stirred
Clock;After be cooled to room temperature discharging, you can obtain polyacrylate dispersion microgel.
1. polyacrylate dispersion microgel performance of table
As shown in Table 1, the polyacrylate dispersion microgel particle diameter that prepared by the inventive method is less;Stability of emulsion compared with
Good, bin stability has exceeded 6 months, can meet normal production storage request;Gel content more than 70%, a side
Face demonstrates the cross-linked structure inside micelle, on the other hand also demonstrates the linear molecule chain structure existed inside micelle;Emulsion
It is uniform after microgel film forming, fine and close, there is no unsound phenomenon after common microgel film forming, water-resistance property of coating is splendid in addition,
After soaking 48 hours in water, film coated surface is non-foaming, film does not fall off, and its good filming performance and water resistance are demonstrated
Unique " the interior crosslinking core-outside line shell " structure of patent microgel of the present invention.This polyacrylate dispersion microgel is expected to application
The contradictory relation of its " Gao Gu " and " low viscous " in water paint, ink system, is solved, and lifts its pseudoplastic behavior energy.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, any modifications and changes made to the present invention both fall within protection scope of the present invention.
Claims (5)
1. a kind of polyacrylate dispersion microgel, it is characterised in that the polyacrylate dispersion microgel is by following weight
The raw material composition of proportioning:2~2.4 parts of anion emulsifier, 1.6~1.8 parts of nonionic emulsifier, pH buffer 0.1~0.2
Part, 1.5~3.3 parts of initiator, 25~35 parts of methyl methacrylate monomer, 65~75 parts of n-butyl acrylate monomer, tertiary fourth
Base hydrogen peroxidase 10 .06~0.08 part, 0.06~0.08 part of rongalite, 114.6~116.5 parts of deionized water;
Also, the polyacrylate dispersion microgel is obtained as follows:
(1) by the anion emulsifier of 2~2.4 weight portions, the nonionic emulsifier of 1.6~1.8 weight portions, 0.1~0.2 weight
The pH buffer of part, the n-butyl acrylate monomer of 5 weight portions are added in the deionized water of 94.1~96 weight portions, 300~
Stir under the conditions of 700rpm and start to warm up, when temperature rises to 82~85 DEG C, velocity modulation will be stirred to 150~250rpm, 4.3 are added
The initiator solution of weight portion, the initiator solution are dissolved in the deionized water of 4 weight portions by the initiator of 0.3 weight portion
In obtain;
(2), after obvious blue light occurs in question response system, the n-butyl acrylate of 55~65 weight portions is dripped in 5~7 hours
Monomer, dripped the methyl methacrylate of the n-butyl acrylate monomer and 25~35 weight portions of 5 weight portions afterwards in 1 hour
The mixed liquor of ester monomer, also, while Deca monomer is started, the initiator solution of 13.7~15.5 weight portion of Deca,
The initiator solution is dissolved in the deionized water of 12.5 weight portions by the initiator of 1.2~3 weight portions and is obtained, and this draws
The time for adding for sending out agent aqueous solution is 6.5~8.5 hours, controls which and drips after complete 0.5 hour in all monomer droppings;
(3) reaction system insulated and stirred was cooled to 65~75 DEG C after 1 hour, added tert-butyl hydroperoxide aqueous solution, the uncle
Butyl peroxy aqueous solution of hydrogen is dissolved in the deionized water of 2 weight portions by the tert-butyl hydroperoxide of 0.06~0.08 weight portion
Obtain, insulated and stirred 10~20 minutes, add rongalite aqueous solution, the rongalite aqueous solution is by 0.06~0.08 weight portion
Rongalite is obtained in being dissolved in the deionized water of 2 weight portions, insulated and stirred 10~20 minutes, is finally down to room temperature discharging, is obtained final product
Described polyacrylate dispersion microgel;
Wherein, the anion emulsifier is any one in PS-625A, PS-625S, PS-725A, PS-725S, PS-925
The mixture of kind or two or more arbitrary proportions;
The nonionic emulsifier is selected from the production of SASOL companiesS70、S90、The mixture of any one or two or more arbitrary proportions in LE407k;
The pH buffer is selected from any one in sodium bicarbonate, sodium carbonate, AMP-95;
The initiator is selected from any one in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
2. polyacrylate dispersion microgel as claimed in claim 1, it is characterised in that described anion emulsifier is
PS-725A。
3. polyacrylate dispersion microgel as claimed in claim 1, it is characterised in that described nonionic emulsifier is
The production of SASOL companiesLE407k。
4. polyacrylate dispersion microgel as claimed in claim 1, it is characterised in that described pH buffer is bicarbonate
Sodium.
5. polyacrylate dispersion microgel as claimed in claim 1, it is characterised in that described initiator is persulfuric acid
Sodium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510108457.9A CN104774287B (en) | 2015-03-12 | 2015-03-12 | Polyacrylate emulsion microgel and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510108457.9A CN104774287B (en) | 2015-03-12 | 2015-03-12 | Polyacrylate emulsion microgel and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104774287A CN104774287A (en) | 2015-07-15 |
CN104774287B true CN104774287B (en) | 2017-04-26 |
Family
ID=53616075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510108457.9A Active CN104774287B (en) | 2015-03-12 | 2015-03-12 | Polyacrylate emulsion microgel and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104774287B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107266625B (en) * | 2017-07-25 | 2019-06-21 | 杭州海维特化工科技有限公司 | A kind of PVC furniture film water inkwood rouge and preparation method thereof |
CN107384011B (en) * | 2017-09-11 | 2020-07-17 | 杭州海维特化工科技有限公司 | PVC floor film gravure printing water-based ink and preparation method thereof |
CN108424488B (en) * | 2018-03-29 | 2020-06-16 | 杭州海维特化工科技有限公司 | Anti-fouling and water-resistant silicone-acrylate emulsion and preparation 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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1974619A (en) * | 2006-11-24 | 2007-06-06 | 东华大学 | Prepn and application of reactive polyacrylate microgel |
CN101864025A (en) * | 2010-06-21 | 2010-10-20 | 东莞市凯迪克高分子材料有限公司 | Preparation method of polyacrylate microgel emulsion and application thereof |
CN103709315A (en) * | 2013-12-04 | 2014-04-09 | 宁波高新区康大美术新材料有限公司 | Highlight acrylic ester emulsion for pigments and preparation method therefor |
-
2015
- 2015-03-12 CN CN201510108457.9A patent/CN104774287B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1974619A (en) * | 2006-11-24 | 2007-06-06 | 东华大学 | Prepn and application of reactive polyacrylate microgel |
CN101864025A (en) * | 2010-06-21 | 2010-10-20 | 东莞市凯迪克高分子材料有限公司 | Preparation method of polyacrylate microgel emulsion and application thereof |
CN103709315A (en) * | 2013-12-04 | 2014-04-09 | 宁波高新区康大美术新材料有限公司 | Highlight acrylic ester emulsion for pigments and preparation method therefor |
Non-Patent Citations (3)
Title |
---|
The role of methyl methacrylate on branching and gel formation in the emulsion copolymerization of BA/MMA;Inigo Gonzalez 等;《Polymer》;20070312;第48卷;第2542-2547页 * |
自交联反应性丙烯酸酯类微凝胶乳液及其涂膜的性能;张静等;《合成橡胶工业》;20090315(第02期);第109-113页 * |
高性能热固型核壳丙烯酸酯乳液的合成及性能研究;钟强锋等;《化学与粘合》;20070915(第05期);第341-345页 * |
Also Published As
Publication number | Publication date |
---|---|
CN104774287A (en) | 2015-07-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104672403B (en) | A kind of environmentally friendly silicone acrylic emulsion and preparation method thereof | |
CN103360561B (en) | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone | |
CN102924646B (en) | Preparation method of waterproof and whiting-resistant silicon-acrylic composite emulsion for interior wall latex coatings | |
WO2017020513A1 (en) | Hydroxyl polyacrylate emulsion and preparation method and application thereof | |
CN104774287B (en) | Polyacrylate emulsion microgel and preparation method thereof | |
CN101781390B (en) | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall | |
CN109824818A (en) | A kind of core-shell structure ambient self cross-linkable acrylic emulsion of multiple cross-linked modification and preparation method thereof | |
CN102898578B (en) | Self-crosslinking silicone-acrylate copolymer emulsion and preparation method | |
CN104530302A (en) | Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion | |
CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
CN108359047B (en) | Graphene-modified water-based acrylate resin and preparation method thereof | |
CN109666111B (en) | Nano SiO2Organosilicon modified acrylate emulsion | |
CN101531736A (en) | Synthetic styrene-acrylic latex | |
CN112851850A (en) | Preparation method of silicon-acrylic emulsion for preparing polymer cement-based waterproof coating | |
CN106632791B (en) | One kind resisting fresh cement accumulation of salt in the surface soil priming paint styrene-acrylic emulsion and preparation method thereof | |
CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
CN106832097B (en) | One kind being based on SiO2PH responsiveness composite microgel and preparation method thereof | |
CN111378075B (en) | Polycarboxylic acid superplasticizer with high slump loss resistance in high-temperature environment and preparation method thereof | |
KR20120008322A (en) | Acrylic emulsion resin having high weather resistance and paint composition comprising the same | |
CN104744623B (en) | A kind of concrete workability conditioning agent and preparation method thereof | |
CN107556429B (en) | Silicone-acrylic emulsion and preparation method thereof | |
CN113755035B (en) | Epoxy silane modified nano alumina and polymer cement-based waterproof coating | |
CN111154029B (en) | Water-based pigment dispersion, preparation method thereof and water-based ink | |
CN108424488A (en) | A kind of anti-pollution, water-fast silicone acrylic emulsion and preparation method thereof | |
CN111087548B (en) | High-gloss quick-drying high-solid-content low-viscosity acrylate emulsion and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
EE01 | Entry into force of recordation of patent licensing contract |