CN101704981B - Cationic polyacrylate emulsion and preparation method thereof - Google Patents
Cationic polyacrylate emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cationic polyacrylate emulsion and a preparation method thereof. The emulsion is prepared by using hydrogenated rosin, azo-bis-isobutyl hydrochloride, emulsifiers, cationic functional monomer, diacetone acrylamide, adipic dihydrazide, acrylic acid and esters, styrene and water as raw materials, and is synthesized by a clearance pre-emulsion polymerization process method; the cationic polyacrylate emulsion includes 45+/- 1 percent of solid content, the pH value of 3-5, the viscosity of 190-220nm and the glass transition temperature of -7 DEG C. The preparation method comprises the following steps: a) raw materials preparation: preparing the raw materials in proportion; b) pre-emulsion preparation; c) seminal emulsion preparation; d) polymerization; e) post-adjustment. The glass transition temperature of the cationic polymer emulsion of the invention is -7 DEG C, which can notably improve the rigidity of cement, and greatly increase the impact resistance of CA mortar; moreover, the cationic polyacrylate emulsion has a stable air content at the same time, which ensures the freeze-thaw stability of the CA mortar. In addition, the cationic polyacrylate emulsion has the advantages of simple and convenient process requirements, and suitability for batch production.
Description
Technical field
The present invention relates to a kind of cationic polyacrylate emulsion and preparation method thereof, be mainly used in modification high-speed railway CA mortar, improve degree of mobilization, shock resistance and the freeze-thaw stability of mortar.
Background technology
The cationic acrylate emulsion is meant polymkeric substance or the copolymer emulsion that the acrylate monomer of employing cationic surfactant or band cationic charge makes, and its essential characteristic is that emulsion particle surface or polymkeric substance itself are positively charged.
The main component of the used CA mortar of high-speed railway is cement, sand, emulsified bitumen.For the stability that guarantees to construct, thereby the emulsified bitumen that great majority adopt all is the emulsified bitumen of cationic, has good stability like this in cement system.Cationic emulsified bitumen can have adequate stability with after cement etc. mixes, and has both guaranteed enough operable times, also guarantees one day early strength requirement.But simple usefulness emulsified bitumen modified CA mortar is awaiting further raising aspect degree of mobilization, shock resistance and the freeze-thaw stability of mortar.
Existing cationic polyacrylate emulsion is applied to papermaking and printing and dyeing usually, because it has the positive charge group, so with electronegative Mierocrystalline cellulose etc. very strong bonding force is arranged, therefore is used as paper strengthening agent in papermaking.The fixation that is used for dyestuff in printing and dyeing can improve its dried, fastness to wet rubbing, especially thioxine dyes to some extent.The 17th the 5th phase of volume of in October, 2000 " dyeing and printing auxiliary " " the synthetic and application of cationic polyacrylate dispersion ", document has been introduced the synthetic of a kind of cationic polyacrylate dispersion, it adopts butyl acrylate, ethyl propenoate, β-Hydroxyethyl acrylate, methyl methacrylate, allyl glycidyl, modified monomer, initiator, reductive agent, PH buffer reagent, acrylamide etc. is raw material, adopt sun/nonionic emulsifying agent system, in suitable PH damping fluid, use oxidation-reduction method, carry out letex polymerization with different initiators and reactive monomer.But because aforesaid propylene acid esters emulsion only adopts is being used of cationic emulsifier and nonionic emulsifying agent, the emulsifying capacity of cationic emulsifier itself very a little less than, thereby can not significantly improve the degree of mobilization of mortar; Expect stable cationic acrylic ester emulsion, promptly obtain the good acrylic ester emulsion of degree of mobilization, just must add a large amount of cationic emulsifiers, but a large amount of emulsifying agents can have influence on the early strength of mortar again greatly.Same reason air content also is closely-related with emulsifier type and consumption, guarantee that stable air content just can have good freeze-thaw stability, but after having added a large amount of emulsifying agents, can guarantee the stable of air content, early strength requirement that but can not guarantee system.Therefore, it can not improve degree of mobilization, shock resistance and the freeze-thaw stability of CA mortar under the prerequisite of proof strength.And be to adopt monomer very early directly to drip method in its building-up process, be difficult to accomplish that emulsifying agent and monomer evenly drip by formula rate, it is quite big to want to produce in suitability for industrialized production batch difficulty of stable emulsion.
Summary of the invention
The present invention aims to provide a kind of cationic polyacrylate emulsion and preparation method thereof, its product energy modification high-speed railway CA mortar, degree of mobilization, shock resistance and the freeze-thaw stability of raising mortar.And its preparation method is suitable for suitability for industrialized production, batch stable.
For achieving the above object, the present invention has adopted following technical scheme: a kind of cationic polyacrylate emulsion, it is characterized in that: it is a raw material with staybelite, azo diisobutyl amidine hydrochloride, emulsifying agent, cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class, vinylbenzene and water, adopts interval type pre-emulsification technology emulsion polymerisation process synthetic; Described cationic polyacrylate emulsion solid content is 45 ± 1%, pH is that 3-5, viscosity are that 100-500mp.s, particle diameter are that 190-220nm, second-order transition temperature are-7 ℃; Described staybelite quality percentage composition is: 1-3%, azo diisobutyl amidine hydrochloride quality percentage composition is 0.1-1%, emulsifying agent quality percentage composition is 0.5-3%, cationic functional monomer mass percentage composition is 1-4%, diacetone-acryloamide(DAA) quality percentage composition is 1.5-3%, two hydrazides quality percentage compositions are 0.5-1.5%, vinylformic acid and ester class quality percentage composition thereof are 25-45%, vinylbenzene quality percentage composition is 5-15%, the quality percentage composition of water is 40-60%.
Described emulsifying agent is cationic emulsifier and nonionic emulsifying agent by mass ratio 1.5-2.5: 1 is composite, described cationic emulsifier is one or more the mixture in dodecyl benzyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, the Trimethyllaurylammonium bromide, and described nonionic emulsifying agent is one or more the mixture in OP-10, OP-40, NP-10, NP-40, the paregal O.Described cationic functional monomer is the mixture of a kind of in dimethylaminoethyl methacrylate, the dimethylaminoethyl acrylate or two kinds.Described two hydrazides are one or more the mixtures in adipic dihydrazide, succinic acid hydrazide ii, sebacic dihydrazide, maleic hydrazide, the ethylene acid hydrazide.Described vinylformic acid and ester class thereof are to be that the ratio of 1-3: 97-99 cooperates and forms by acrylic acid or the like and ester class in mass ratio; Described acrylic acid or the like is the mixture of a kind of in vinylformic acid, the methacrylic acid or two kinds, and described ester class is one or more the mixture in methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, the Isooctyl acrylate monomer.
The preparation method of above-mentioned cationic polyacrylate emulsion, it may further comprise the steps:
A) preparation of raw material: amount is prepared staybelite, azo diisobutyl amidine hydrochloride, emulsifying agent, cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class, vinylbenzene and water raw material in proportion;
B) preparation of pre-emulsion: with quality in the raw material is the water input header tank of 30-50%, quality is the emulsifying agent of 70-98% in the adding raw material, whole staybelite, vinylformic acid and ester class thereof, vinylbenzene, diacetone-acryloamide(DAA), cationic functional monomer and carry out emulsification in the raw material obtains pre-emulsion;
C) preparation of seed emulsion: remaining water is added in the reactor, and the remaining emulsifying agent of adding, after being warming up to 65-70 ℃, the quality that adding is made by step b is that quality is the azo diisobutyl amidine hydrochloride of 25-50% in the pre-emulsion of 5-20% and the raw material, reacting by heating 10-20min, be warming up to 75-80 ℃ of reaction for some time again, faint blue light appears in emulsion, then makes seed emulsion;
D) polymerization: in the prepared seed emulsion of step b, temperature of reaction maintains 75-80 ℃, in 3-5 hour, remaining pre-emulsion and remaining azo diisobutyl amidine hydrochloride evenly be added drop-wise in the reactor and react, continued again after dropwising insulation reaction 1-2 hour, and obtained the cationic polyacrylate emulsion crude product;
E) back is adjusted: the cationic polyacrylate emulsion crude product is cooled to is not higher than 45 ℃, add two whole hydrazides in the raw material, adding small amount of alkali, to regulate pH be 3-5, and filtering filtrate is the cationic polyacrylate emulsion finished product, and its solid content is 45 ± 1%.
Cationic polyacrylate emulsion of the present invention adopts pre-emulsification seeded emulsion polymerization, and with respect to early stage monomer dropping method, processing requirement of the present invention is simple, convenient, be easy to produce in batches, and the Environmental Safety height, the product batches circulation ratio is strong.In emulsion, introduce cationic functional monomer dimethylaminoethyl methacrylate or dimethylaminoethyl acrylate, adopt nonionic and cationic emulsifier composite, and added the staybelite resin and come modified acrylate emulsion as primary emulsion.Cationic functional monomer and rosiny are introduced the consumption that can reduce emulsifying agent, have improved the stability of system, have guaranteed the degree of mobilization of CA mortar; System employing nonionic and cationic emulsifier are composite as primary emulsion, rosiny is introduced the bleed effect that has increased system, the air content quite stable of system makes the pore that contains uniform and smooth in the CA mortar, guarantees the requirement of the freeze-thaw stability of later stage in using; The monomeric introducing of cold cross-linking, by the normal temperature polymer crosslinked action of active carbonyl compound and hydrazides, make whole system in dehydration process further by crosslinked raising early strength; The second-order transition temperature of this cationic polymer emulsion is-7 degree, is to be in high-elastic rubbery state at normal temperatures, and it can well improve the rigidity of cement, has improved the shock resistance of CA mortar greatly.Thereby the cationic acrylate emulsion that synthesizes both had good stability and also had very high early strength, and stable air content is arranged simultaneously, guaranteed the freeze-thaw stability of CA mortar.
The index that experimental results show that cationic polyacrylate emulsion of the present invention is as follows:
Solid content (%) 45 ± 1%
PH 3-5
Viscosity (mp.s) 100-500mp.s
Particle diameter (nm) 190-220nm
T gram (℃)-7 ℃
It is as follows to be applied in the application indexes that is reached in the CA mortar:
Embodiment
Cationic polyacrylate emulsion of the present invention, with staybelite, emulsifying agent, azo diisobutyl amidine hydrochloride, (in the present invention as initiator), cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class, vinylbenzene and water are raw material, adopt interval type pre-emulsification technology emulsion polymerisation process synthetic; Described cationic polyacrylate emulsion solid content is 45 ± 1%, PH is that 3-5, viscosity are that 100-500mp.s, particle diameter are that 190-220nm, second-order transition temperature are-7 ℃; Described staybelite quality percentage composition is: 1-3%, azo diisobutyl amidine hydrochloride quality percentage composition is 0.1-1%, emulsifying agent quality percentage composition is 0.5-3%, cationic functional monomer mass percentage composition is 1-4%, diacetone-acryloamide(DAA) quality percentage composition is 1.5-3%, two hydrazides quality percentage compositions are 0.5-1.5%, vinylformic acid and ester class quality percentage composition thereof are 25-45%, vinylbenzene quality percentage composition is 5-15%, the quality percentage composition of water is 40-60%.
Described emulsifying agent is cationic emulsifier and nonionic emulsifying agent by 1.5-2.5: 1 is composite, described cationic emulsifier is one or more the mixture in dodecyl benzyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, the Trimethyllaurylammonium bromide, and described nonionic emulsifying agent is one or more the mixture in OP-10, OP-40, NP-10, NP-40, the paregal O.
Described cationic functional monomer is the mixture of a kind of in dimethylaminoethyl methacrylate, the dimethylaminoethyl acrylate or two kinds.
Described two hydrazides are one or more the mixtures in adipic dihydrazide, succinic acid hydrazide ii, sebacic dihydrazide, maleic hydrazide, the ethylene acid hydrazide.
Described vinylformic acid and ester class thereof are to be that the ratio of 1-3: 97-99 cooperates and forms by acrylic acid or the like and ester class in mass ratio; Described acrylic acid or the like is the mixture of a kind of in vinylformic acid, the methacrylic acid or two kinds, and described ester class is one or more the mixture in methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, the Isooctyl acrylate monomer.
Cationic polyacrylate emulsion preparation method of the present invention, it may further comprise the steps:
A) preparation of raw material and preparation
Staybelite: adopt commercially available staybelite, the staybelite of the technical grade of producing as the upright gloomy chemical industry in Shanghai company limited.
Azo diisobutyl amidine hydrochloride:, adopt the commercial grade industrial goods to get final product as initiator.
Emulsifying agent: cationic emulsifier and nonionic emulsifying agent are pressed mass ratio 1.5-2.5: 1 is composite, described cationic emulsifier is one or more the mixture in dodecyl benzyl dimethyl ammonium chloride (1227), Dodecyl trimethyl ammonium chloride (1231), the Trimethyllaurylammonium bromide (1232), and described nonionic emulsifying agent is one or more the mixture in OP-10, OP-40, NP-10, NP-40, the paregal O.The specific embodiment of emulsifying agent preparation sees the following form:
| Embodiment | Cationic emulsifier | Nonionic emulsifying agent | The mass ratio of cationic emulsifier and nonionic emulsifying agent |
| 1 | 1227 | OP-10, OP-40, NP-10 mixture | 1.5∶1 |
| 2 | 1231 | OP-40, NP-10 mixture | 2.5∶1 |
| 3 | 1232 | NP-10 | 2.0∶1 |
| 4 | 1227,1231 mixtures | NP-40 | 2.5∶1 |
| 5 | 1227,1232 mixtures | Paregal O | 1.8∶1 |
| 6 | 1227,1231,1232 mixtures | OP-10 | 2.0∶1 |
The cationic functional monomer: the cationic functional monomer is the mixture of a kind of in dimethylaminoethyl methacrylate, the dimethylaminoethyl acrylate or two kinds.Dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate all can adopt commercially available technical grade product.
Diacetone-acryloamide(DAA): the product that can adopt Wuxi City Liang Xi Fine Chemical Co., Ltd to produce.
Two hydrazides: be one or more the mixture in adipic dihydrazide, succinic acid hydrazide ii, sebacic dihydrazide, maleic hydrazide, the ethylene acid hydrazide.
Vinylformic acid and ester class thereof: vinylformic acid and ester class thereof are to be that the ratio of 1-3: 97-99 cooperates and forms by acrylic acid or the like and ester class in mass ratio.Described acrylic acid or the like is the mixture of a kind of in vinylformic acid, the methacrylic acid or two kinds, and described ester class is one or more the mixture in methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, the Isooctyl acrylate monomer.The specific embodiment of vinylformic acid and the preparation of ester class thereof sees the following form:
| Embodiment | Acrylic acid or the like | The ester class | The mass ratio of vinylformic acid and ester class thereof |
| 1 | Vinylformic acid | Methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, Isooctyl acrylate monomer mixture | 1∶99 |
| 2 | Methacrylic acid | Methyl methacrylate | 3∶97 |
| 3 | Vinylformic acid, methacrylic acid mixture | Butyl acrylate | 2∶98 |
| 4 | Vinylformic acid | Methyl acrylate, butyl acrylate mixture | 1.5∶98.5 |
| 5 | Methacrylic acid | Methyl methacrylate, ethyl propenoate mixture | 2∶98 |
| 6 | Vinylformic acid, methacrylic acid mixture | Isooctyl acrylate monomer | 1∶99 |
Vinylbenzene: the product that can adopt Wuxi City Liang Xi Fine Chemical Co., Ltd.
Water: deionized water.
With above-mentioned staybelite, azo diisobutyl amidine hydrochloride, emulsifying agent, the cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class thereof, vinylbenzene and water, prepare standby in following ratio: staybelite quality percentage composition is: 1-3%, azo diisobutyl amidine hydrochloride quality percentage composition is 0.1-1%, emulsifying agent quality percentage composition is 0.5-3%, cationic functional monomer mass percentage composition is 1-4%, diacetone-acryloamide(DAA) quality percentage composition is 1.5-3%, two hydrazides quality percentage compositions are 0.5-1.5%, vinylformic acid and ester class quality percentage composition thereof are 25-45%, vinylbenzene quality percentage composition is 5-15%, the quality percentage composition of water is 40-60%.
The quality percentage composition ratio of concrete each raw material sees the following form:
| Embodiment | Staybelite | Initiator | Emulsifying agent | The cationic functional monomer | Diacetone-acryloamide(DAA) | Two hydrazides | Vinylformic acid and ester class thereof | Vinylbenzene | Water |
| 1 | 1 | 0.6 | 3 | 4 | 3 | 1.5 | 30 | 10 | 46.9 |
| 2 | 3 | 0.1 | 0.5 | 1 | 1.5 | 0.5 | 45 | 5 | 43.4 |
| 3 | 2 | 0.5 | 1 | 3 | 2 | 1 | 25 | 5.5 | 60 |
| 4 | 1 | 0.8 | 1.5 | 1 | 1 | 0.5 | 40 | 15 | 39.2 |
| 5 | 1.5 | 0.2 | 2 | 2 | 2.5 | 1 | 30 | 10 | 40.8 |
| 6 | 1 | 0.4 | 1 | 1 | 1 | 1 | 30 | 9.6 | 50 |
| 7 | 2 | 1 | 2.5 | 2 | 2 | 1 | 28 | 10 | 51.5 |
Quality percentage composition ratio by above each raw material all has reasonable effect according to the prepared cationic polyacrylate emulsion of the inventive method.
B) preparation of pre-emulsion
With quality in the raw material is the water input header tank of 30-50%, can be 30% or 50% or 45% or 40%, quality is the emulsifying agent (as 70%, 98%, 90%, 80%) of 70-98% in the adding raw material, add staybelites whole in the raw material, vinylformic acid and ester class thereof, vinylbenzene, diacetone-acryloamide(DAA), cationic functional monomer again and carry out emulsification, obtain pre-emulsion;
C) preparation of seed emulsion
Remaining water is added in the reactor, and the remaining emulsifying agent of adding, after being warming up to 65-70 ℃, the quality that adding is made by step b is that quality is the initiator (as 50%, 25%, 30%) of 25-50% in the pre-emulsion of 5-20% (as 5%, 20%5,10%, 10%) and the raw material, reacting by heating 10-20 minute (as 10 minutes, 20 minutes, 150 minutes), be warming up to 75-80 ℃ (as 75 ℃, 80 ℃, 78 ℃) again, be reacted to emulsion and faint blue light occurs, then make seed emulsion;
D) polymerization
In the prepared seed emulsion of step b, temperature of reaction maintains 75-80 ℃, (can be 3 hours or 4 hours or 5 hours) evenly be added drop-wise to residual monomer pre-emulsion and remaining initiator in the reactor and reacts in 3-5 hour, continued again after dropwising insulation reaction 1-2 hour, and obtained the cationic polyacrylate emulsion crude product;
E) back is adjusted
The cationic polyacrylate emulsion crude product is cooled to is not higher than 45 ℃, add two whole hydrazides in the raw material, adding small amount of alkali, to regulate PH be 3-5 (can 3 or 4 or 5), and filtering filtrate is the cationic polyacrylate emulsion finished product, and its solid content is 45 ± 1%.
Illustrated with a specific examples below:
Embodiment 1:
Drop into deionized water 195 grams under the room temperature in 1k gram four-hole reaction flask, emulsifying agent 25 grams (wherein cationic emulsifier 122718 grams, nonionic emulsifying agent OP-107 gram) stir; With vinylformic acid and ester class thereof 319.9 grams (wherein monomers methyl methacrylate 82.8 grams, butyl acrylate 230.8 grams, vinylformic acid 6.3 grams), vinylbenzene 60.2 grams, diacetone-acryloamide(DAA) 15.8 grams, cationic functional monomer (dimethylaminoethyl methacrylate) 11.7 grams, staybelite 10.6 grams mix; Under the situation of stirring and emulsifying agent mixed aqueous solution, slowly add mix monomer, high-speed stirring 25min fast.Obtain pre-emulsion 645 grams.
6 gram azo diisobutyl amidine hydrochlorides are dissolved in the 45 gram deionized waters; In the four-hole reaction flask of 1000 grams, add 304 gram deionized waters and nonionic emulsifying agent OP-10 2 grams simultaneously, be warming up to 68 ℃, drop into the 32.1 gram pre-emulsions and the above-mentioned 20 gram azo diisobutyl amidine hydrochloride aqueous solution in the reaction flask together again, reacting by heating 15 minutes, be warming up to 78 ℃ of reactions again, treat that faint blue light appears in emulsion, then makes seed emulsion.
In 4 hours residual monomer pre-emulsion and initiator evenly be added drop-wise in the reactor then and react, temperature of reaction maintains 78 ℃; Continued insulation reaction after dropwising again 2 hours; Cool to 20 ℃, add 9 gram adipic dihydrazides, add less ammonia and regulate pH3-5, solid content 45 ± 1% filters.
Embodiment 2:
Drop into deionized water 183 grams under the room temperature in 1k gram four-hole reaction flask, emulsifying agent 18 grams (wherein cationic emulsifier 1,231 14 grams, nonionic emulsifying agent NP-10 4 grams) stir; With vinylformic acid and ester class 292.7 grams (wherein monomers methyl methacrylate 49.5 grams, Isooctyl acrylate monomer 134.2 grams, butyl acrylate 129.6 grams) thereof, vinylbenzene 79.4 grams, vinylformic acid 9.1 grams, diacetone-acryloamide(DAA) 16.8 grams, cationic functional monomer (dimethylaminoethyl acrylate) 12.7 grams, staybelite 15.6 grams mix; Under the situation of stirring and emulsifying agent mixed aqueous solution, slowly add mix monomer, high-speed stirring 20-30min fast.Obtain pre-emulsion 627 grams.
8 gram azo diisobutyl amidine hydrochlorides are dissolved in the 40 gram deionized waters; In the four-hole reaction flask of 1k gram, add 321 gram deionized waters and cationic emulsifier 1,231 1 grams and nonionic emulsifying agent NP-102 gram simultaneously, be warming up to 68 ℃, drop into the 43.5 gram pre-emulsions and the above-mentioned 17 gram azo diisobutyl amidine hydrochloride aqueous solution in the reaction flask together again, reacting by heating 15 minutes, be warming up to 78 ℃ of reactions again, treat that faint blue light appears in emulsion, then makes seed emulsion.
In 4 hours residual monomer pre-emulsion and initiator evenly be added drop-wise in the reactor then and react, temperature of reaction maintains 78 ℃; Continued insulation reaction after dropwising again 2 hours; Cool to 20 ℃, add 7 gram sebacic dihydrazides, add less ammonia and regulate pH3-5, solid content 45 ± 1% filters.
Claims (4)
1. cationic polyacrylate emulsion, it is characterized in that: it is a raw material with staybelite, azo diisobutyl amidine hydrochloride, emulsifying agent, cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class, vinylbenzene and water, adopts interval type pre-emulsification technology emulsion polymerisation process synthetic; Described cationic polyacrylate emulsion solid content is 45 ± 1%, pH is that 3-5, viscosity are that 100-500mp.s, particle diameter are that 190-220nm, second-order transition temperature are-7 ℃; Described staybelite quality percentage composition is: 1-3%, azo diisobutyl amidine hydrochloride quality percentage composition is 0.1-1%, emulsifying agent quality percentage composition is 0.5-3%, cationic functional monomer mass percentage composition is 1-4%, diacetone-acryloamide(DAA) quality percentage composition is 1.5-3%, two hydrazides quality percentage compositions are 0.5-1.5%, vinylformic acid and ester class quality percentage composition thereof are 25-45%, vinylbenzene quality percentage composition is 5-15%, the quality percentage composition of water is 40-60%; Described emulsifying agent is cationic emulsifier and nonionic emulsifying agent by mass ratio 1.5-2.5: 1 is composite, described cationic emulsifier is one or more the mixture in dodecyl benzyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, the Trimethyllaurylammonium bromide, and described nonionic emulsifying agent is one or more the mixture in OP-10, OP-40, NP-10, NP-40, the paregal O; Described cationic functional monomer is the mixture of a kind of in dimethylaminoethyl methacrylate, the dimethylaminoethyl acrylate or two kinds.
2. by the described cationic polyacrylate emulsion of claim 1, it is characterized in that described two hydrazides are one or more the mixtures in adipic dihydrazide, succinic acid hydrazide ii, sebacic dihydrazide, maleic hydrazide, the ethylene acid hydrazide.
3. by the described cationic polyacrylate emulsion of claim 1, it is characterized in that described vinylformic acid and ester class thereof are is that the ratio of 1-3: 97-99 cooperates and forms by acrylic acid or the like and ester class in mass ratio; Described acrylic acid or the like is the mixture of a kind of in vinylformic acid, the methacrylic acid or two kinds, and described ester class is one or more the mixture in methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, ethyl propenoate, the Isooctyl acrylate monomer.
4. by the preparation method of the described cationic polyacrylate emulsion of claim 1, it is characterized in that it may further comprise the steps:
A) preparation of raw material: amount is prepared staybelite, azo diisobutyl amidine hydrochloride, emulsifying agent, cationic functional monomer, diacetone-acryloamide(DAA), two hydrazides, vinylformic acid and ester class, vinylbenzene and water raw material in proportion;
B) preparation of pre-emulsion: with quality in the raw material is the water input header tank of 30-50%, quality is the emulsifying agent of 70-98% in the adding raw material, whole staybelite, vinylformic acid and ester class thereof, vinylbenzene, diacetone-acryloamide(DAA), cationic functional monomer and carry out emulsification in the raw material obtains pre-emulsion;
C) preparation of seed emulsion: remaining water is added in the reactor, and the remaining emulsifying agent of adding, after being warming up to 65-70 ℃, the quality that adding is made by step b is that quality is the azo diisobutyl amidine hydrochloride of 25-50% in the pre-emulsion of 5-20% and the raw material, reacting by heating 10-20min, be warming up to 75-80 ℃ of reaction for some time again, faint blue light appears in emulsion, then makes seed emulsion;
D) polymerization: in the prepared seed emulsion of step b, temperature of reaction maintains 75-80 ℃, in 3-5 hour, remaining pre-emulsion and remaining azo diisobutyl amidine hydrochloride evenly be added drop-wise in the reactor and react, continued again after dropwising insulation reaction 1-2 hour, and obtained the cationic polyacrylate emulsion crude product;
E) back is adjusted: the cationic polyacrylate emulsion crude product is cooled to is not higher than 45 ℃, add two whole hydrazides in the raw material, adding small amount of alkali, to regulate pH be 3-5, and filtering filtrate is the cationic polyacrylate emulsion finished product, and its solid content is 45 ± 1%.
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| CN103059212B (en) * | 2012-12-25 | 2014-11-05 | 中科院广州化学有限公司 | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof |
| CN103183491B (en) * | 2013-03-20 | 2015-10-28 | 嘉兴市广兴建材科技有限公司 | The preparation method of crosslinking polymer cement waterproofing paint |
| CN103232709B (en) * | 2013-04-27 | 2016-06-01 | 山西省交通科学研究院 | A kind of rubber powder modified asphalt linking agent and its preparation method |
| CN108892749B (en) * | 2018-06-22 | 2020-07-10 | 杭州科润生物科技有限公司 | Cationic system polyacrylic acid and preparation method and application thereof |
| CN111576082A (en) * | 2020-04-23 | 2020-08-25 | 上海东升新材料有限公司 | Cation dispersed rosin size and preparation method thereof |
| CN117567912B (en) * | 2023-11-22 | 2024-05-28 | 江西科技师范大学 | Recyclable polyacrylate emulsion coating and preparation method and application thereof |
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2009
- 2009-11-26 CN CN2009101539278A patent/CN101704981B/en not_active Expired - Fee Related
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