CN105669914A - Freeze-thaw stable type acrylate polymer emulsion and method for preparing same - Google Patents
Freeze-thaw stable type acrylate polymer emulsion and method for preparing same Download PDFInfo
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Abstract
The invention discloses freeze-thaw stable type acrylate polymer emulsion and a method for preparing the same. The freeze-thaw stable type acrylate polymer emulsion comprises 6.8-14wt% of unsaturated carboxylic acid monomers, 14-21.5wt% of C1-C5 unsaturated carboxylate ester, 3-6.5wt% of polymerizable anionic bisamide surfactants, 0-0.8wt% of non-polymerizable anionic surfactants, 0.05-0.1wt% of initiators, 0.05-0.25wt% of cross-linking agents, 0.4-0.9wt% of pH (potential of hydrogen) buffer agents and the balance deionized water. The unsaturated carboxylic acid monomers, the C1-C5 unsaturated carboxylate ester, the polymerizable anionic bisamide surfactants, the non-polymerizable anionic surfactants, the initiators, the cross-linking agents, the pH buffer agents and the deionized water are subjected to emulsion polymerization to obtain the freeze-thaw stable type acrylate polymer emulsion. The freeze-thaw stable type acrylate polymer emulsion and the method have the advantages that the freeze-thaw stable type acrylate polymer emulsion is good in suspension ability, transparency and freeze-thaw stability, high in thickening ability and short in freeze-thaw recovery time, and the like.
Description
Technical field
The present invention relates to a kind of freeze-thaw stable type acrylate polymer emulsion and preparation method thereof, belong to Polymer Synthesizing field. Described acrylate polymer emulsion has the advantages such as suspending power is good, thickening capabilities strong, the transparency is good, the freeze/thaw recovery time is short, freeze-thaw stability is good.
Background technology
Acrylate polymer emulsion is mainly used in the fields such as exterior coating, leather finish, textile finishing, binding agent, papermaking, personal care articles, domestic and industrial cleaners; But traditional acrylate polymer emulsion is generally with water for solvent, the meeting freeze agglomeration when low temperature, and lose use value. Freeze thawing unstability brings many difficulties to acrylate polymer emulsion product in production, transport, storage and the application of cold district (lower than 0 DEG C).
The preparation method that CN201410023820.2 discloses a kind of frost resistance acrylate suspension thickening agent emulsion, employing is that chain alkyl polyoxyethylene ether esters of acrylic acid is as special function monomer. After adopting chain alkyl polyoxyethylene ether esters of acrylic acid as special function monomer, its anti-freezing property is effectively improved, according to the performance data of its record it can be seen that it is placed in the environment of subzero 5 DEG C after three months to take out and still can use.
CN201410294831.4 discloses a kind of styrene-acrylic emulsion with excellent freeze-thaw stability in paint field application. It adopts anion emulsifier and nonionic emulsifier 5 to join to have reached good cryoprotective effects.
CN201410604436.1 discloses a kind of with acrylate for principal monomer, is C with formula10-15H22-32O(CH2CH2O)xThe secondary alcohol ethoxyl compound of H has been obtained by reacting the paint formulations that a kind of freeze thawing is effective, and its freeze thawing effect is that after freeze-thaw cycle 3 times, viscosity conservation rate is 90% when-10 DEG C.
CN201510514894.0 discloses a kind of internal wall emulsion coating with excellent freeze-thaw stability, it adopts styrene-acrylate emulsion and anion-nonionic composite diffusion wetting agent as primary raw material, and when-10 DEG C, the KU value after freeze-thaw cycle 10 times is almost constant.
But current freeze-thaw stable type acrylate polymer emulsion ubiquity some shortcomings, as thickening capabilities is poor, poor transparency, the problems such as weatherability is poor, freeze/thaw recovery time length.
Summary of the invention
It is an object of the invention to provide a kind of freeze-thaw stable type acrylate polymer emulsion and preparation method thereof, this acrylate polymer emulsion has the advantages such as suspending power is good, thickening capabilities strong, the transparency is good, the freeze/thaw recovery time is short, freeze-thaw stability is good.The present invention adopts the polymerisable anionic bisamide of macromole as emulsifying agent, first prepare core seed emulsion, preparing hud typed acrylate polymer emulsion again, prepared polymer emulsion has the advantages such as suspending power is good, thickening capabilities strong, the transparency is good, the freeze/thaw recovery time is short, freeze-thaw stability is good.
For realizing object above, the technical scheme is that a kind of freeze-thaw stable type acrylate polymer emulsion preparation method, obtained through emulsion polymerization by following components:
Unsaturated carboxylic acid monomer 6.8～14wt%;
Esters of unsaturated carboxylic acids 14～the 21.5wt% of C1-C5;
Polymerisable anionic bisamide surfactant 3～6.5wt%;
Non-polymerisable anionic surfactant 0～0.8wt%
Initiator 0.05～0.1wt%;
Cross-linking agent 0.05～0.25wt%;
PH buffer agent 0.4～0.9wt%;
And the deionized water of surplus;
Described polymerisable anionic bisamide surfactant is below general formula:
R1Alkyl or benzene alkyl for C6～C8;
R2The alkylene containing unsaturated double-bond for C2～C5;
R3For the alkylsulfonate of C1～C5, carboxylate;
N, m are 10～30.
At above-mentioned freeze thawing excellent effect, have in the preparation method of alkali-soluble acrylate's polymer of efficient thickening capabilities, comprise the following steps:
Step 1: polymerisable anionic bisamide surfactant, non-polymerisable anionic surfactant, pH buffer agent are dissolved in deionized water, are warming up to 80 DEG C～90 DEG C under the protection of noble gas;
Step 2: monomer phase will be formed after the esters of unsaturated carboxylic acids of C1-C5, unsaturated carboxylic acid monomer, cross-linking agent mix homogeneously;
Step 3: preparation initiator solution;
Step 4: add the monomer phase of 19.5wt%～25wt% and the initiator of 8.5wt%～9.1wt% in the solution of step 1, start after 5min～30min to drip remaining initiator solution and remaining monomer phase, dropping 150min～200min dropwises to initiator mutually with monomer, is incubated 3h～6h;
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, described unsaturated carboxylic acid monomer is at least one in acrylic acid, methacrylic acid, itaconic acid, fumaric acid .beta.-methylacrylic acid, equisetic acid, maleic acid.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, the esters of unsaturated carboxylic acids of described C1-C5 is at least one of the Arrcostab of the C1～C5 of acrylic or methacrylic acid.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, the esters of unsaturated carboxylic acids of described C1-C5 is the mixture of at least one and 2-(Acryloyloxy)ethanol of the Arrcostab of the C1～C5 of acrylic or methacrylic acid.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, described cross-linking agent is diallyl phthalate, diallyl phthalate or diallyl itaconate.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, described initiator is Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, described pH buffer agent is sodium bicarbonate, triethanolamine or triethylamine.
In the preparation method of above-mentioned freeze-thaw stable type acrylate polymer emulsion, non-polymerisable anionic surfactant is dodecylbenzene sodium sulfonate, sodium lauryl sulphate.
The invention have the benefit that
The present invention is prepared by emulsion polymerization, by adding the polymerizable negative ion type bisamide surfactant of macromole, prepares a kind of novel hydrophobic association type alkali-soluble acrylate's polymer emulsion. Except carboxyl launches the coulomb that produces inside and outside, hydrophobic group in molecule and the different intermolecular associations that can occur, forms three-dimensional physical space network structure, and the thickening efficiency making thickening agent is higher, and freeze thawing is effective. And the polymerisable anionic bisamide surfactant of the high molecular introduced, compared with other micromolecular polymerisable surfactant, can more effectively reduce the surface activity tension force of water, there is less critical micelle concentration, higher absorption property, the more important thing is that the present invention joins in moisture surfactant system, excellent thickening suspendability and the transparency can be shown, there is the features such as freeze-thaw stability is good, the freeze/thaw recovery time is short simultaneously.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme is described in further detail, but does not constitute any limitation of the invention.
Embodiment 1
The preparation of polymerisable anionic bisamide surfactant: by instruments such as four-hole bottle, agitator, charge pipes in 120 DEG C of dry 3h, takes out and is placed in exsiccator, uses after cooling. To with agitator, thermometer four-hole bottle in add 17.42g toluene di-isocyanate(TDI) (TDI), then dropping 102.8g sulfonate sodium polyethers (A), after reaction 2h, the lower heating of stirring is to 40 DEG C, add appropriate dibutyl tin laurate and make catalyst, then drip the polyethers (B) of 92.4g.
Continue reaction 2h. Being subsequently cooled to 30 DEG C, add distilled water stirring 0.5h, the concentration adding distilled water and surfactant solution is 30wt%, namely prepares polymerizable bisamide surfactant (C).
N is 20, m is 20.
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1051g deionized water, 48g polymerizable bisamide surfactant (C), 10g sodium bicarbonate, obtain after agitated table live emulsion; In five mouthfuls of flasks with agitating device of another 2L, add 200g ethyl acrylate, 68g butyl acrylate, 40g methyl methacrylate, 30g 2-(Acryloyloxy)ethanol, 1g diallyl phthalate, 100g acrylic acid, 12g methacrylic acid, agitated obtain monomer phase; 0.1g potassium peroxydisulfate is dissolved in 5g deionized water and obtains initiator solution A, 1g potassium peroxydisulfate is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 80 DEG C, add 90g monomer phase, initiator solution A is added after 1min, become after blue 15min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 200min and 198min respectively, after monomer phase and initiator solution dropwise, it is incubated 6h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Embodiment 2
The preparation of polymerisable anionic bisamide surfactant: by instruments such as four-hole bottle, agitator, charge pipes in 120 DEG C of dry 3h, takes out and is placed in exsiccator, uses after cooling. To with agitator, thermometer four-hole bottle in add 17.42g toluene di-isocyanate(TDI), then dropping 56.8g sodium sulfate salt polyethers (A). After reaction 2h, the lower heating of stirring is to 40 DEG C, and adding appropriate dibutyl tin laurate makes catalyst, then drips the polyethers (B) of 61.4g.
Continue reaction 2h. Being subsequently cooled to 30 DEG C, add distilled water stirring 0.5h, the concentration at addition distilled water rear surface activating agent is 30%, namely prepares polymerizable bisamide surfactant (C).
N is 10, m is 12.
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1051g deionized water, 48g polymerizable bisamide surfactant (C), 10g sodium bicarbonate, agitated obtain table live emulsion; In five mouthfuls of flasks with agitating device of another 2L, addition 200g ethyl acrylate, 70g methyl methacrylate, 68g butyl acrylate, 1g diallyl phthalate, 100g acrylic acid, the stirring of 12g methacrylic acid obtain monomer phase; 0.1g potassium peroxydisulfate is dissolved in 5g deionized water and obtains initiator solution A, 1g potassium peroxydisulfate is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 90 DEG C, add 90g monomer phase, initiator solution A is added after 1min, become after blue 15min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 182min and 180min respectively, after monomer phase and initiator solution dropwise, it is incubated 3h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Embodiment 3
The preparation of polymerisable anionic bisamide surfactant: by instruments such as four-hole bottle, agitator, charge pipes in 120 DEG C of dry 3h, takes out and is placed in exsiccator, uses after cooling. To with agitator, thermometer four-hole bottle in add 16.82g hexamethylene diisocyanate (HDI), then dropping 135.8g carboxylic acid sodium salt polyethers (A), after reaction 2h, the lower heating of stirring is to 40 DEG C, add appropriate dibutyl tin laurate and make catalyst, then drip the polyethers (B) of 139.2g.
Continue reaction 2h. Being subsequently cooled to 30 DEG C, add distilled water stirring 0.5h, the concentration at addition distilled water rear surface activating agent is 30%, namely prepares polymerizable bisamide surfactant (C).
N is 28, m is 30.
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1038g deionized water, 53g polymerizable bisamide surfactant (C), 12g dodecylbenzene sodium sulfonate, 8g triethanolamine obtain table and live emulsion; 100g ethyl acrylate, 68g butyl acrylate, 30g acrylic acid methyl ester. is added in five mouthfuls of flasks with agitating device of another 2L, 40g 2-(Acryloyloxy)ethanol, 1.1g diallyl phthalate, 120g acrylic acid, 92g methacrylic acid, agitated obtain monomer phase; Sodium peroxydisulfate 0.12g is dissolved in 6g deionized water and obtains initiator solution A, 1.2g sodium peroxydisulfate is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 85 DEG C, add 112.5g monomer phase, initiator solution A is added after 1min, become after blue 15min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 152min and 150min respectively, after monomer phase and initiator solution dropwise, it is incubated 5h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Embodiment 4
The preparation of polymerisable anionic bisamide surfactant: by instruments such as four-hole bottle, agitator, charge pipes in 120 DEG C of dry 3h, takes out and is placed in exsiccator, uses after cooling. To with agitator, thermometer four-hole bottle in add 17.42g toluene di-isocyanate(TDI), then dropping 99.2g carboxylic acid sodium salt polyethers (A), after reaction 2h, the lower heating of stirring is to 40 DEG C, add appropriate dibutyl tin laurate and make catalyst, then drip the polyethers (B) of 96.6g.
Continue reaction 2h. Being subsequently cooled to 30 DEG C, add distilled water stirring 0.5h, the concentration at addition distilled water rear surface activating agent is 30%, namely prepares polymerizable bisamide surfactant (C).
N is 20, m is 20.
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1032g deionized water, 107g polymerizable bisamide surfactant (C), 10g triethanolamine, agitated obtain table live emulsion; In five mouthfuls of flasks with agitating device of another 2L, add 130g ethyl acrylate, 68g butyl acrylate, 50g methyl methacrylate, 40g 2-(Acryloyloxy)ethanol, 2.1g diallyl itaconate, 120g acrylic acid, 42g methacrylic acid, agitated obtain monomer phase; 0.12g Ammonium persulfate. is dissolved in 5g deionized water and obtains initiator solution A, 1.3g Ammonium persulfate. is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 83 DEG C, add 112.5g monomer phase, initiator solution A is added after 1min, become after blue 15min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 162min and 160min respectively, after monomer phase and initiator solution dropwise, it is incubated 4h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Embodiment 5
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1032g deionized water, 107g polymerizable bisamide surfactant, 15g triethanolamine, agitated obtain table live emulsion; Polymerizable bisamide surfactant in the present embodiment is identical with the polymerizable bisamide surfactant in embodiment 3, and in five mouthfuls of flasks with agitating device of another 2L, addition 130g ethyl acrylate, 68g butyl acrylate, 50g methyl methacrylate, 40g Hydroxypropyl acrylate, 4.2g diallyl itaconate, 120g acrylic acid, the stirring of 42g methacrylic acid obtain monomer phase; 0.36g sodium peroxydisulfate is dissolved in 5g deionized water and obtains initiator solution A, 1.3g sodium peroxydisulfate is dissolved in 68g deionized water and obtains initiator solution-B;
Emulsion of being lived by table is heated to 87 DEG C, add 90g monomer phase, initiator solution A is added after 1min, become after blue 20min until aqueous phase, at the uniform velocity dropping initiator solution B and 2.6g sodium sulfite, starts at the uniform velocity dropping monomer phase, respectively dropping 162min and 160min after 2min, after monomer phase and initiator solution dropwise, it is incubated 3h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Embodiment 6
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1032g deionized water, 107g polymerizable bisamide surfactant, 10g triethanolamine, agitated obtain table live emulsion; Polymerizable bisamide surfactant in the present embodiment is identical with the polymerizable bisamide surfactant in embodiment 1, and in five mouthfuls of flasks with agitating device of another 2L, addition 130g ethyl acrylate, 68g butyl acrylate, 50g methyl methacrylate, 40g 2-(Acryloyloxy)ethanol, 2.1g diallyl itaconate, 120g acrylic acid, the stirring of 42g methacrylic acid obtain monomer phase; 0.12g Ammonium persulfate. is dissolved in 5g deionized water and obtains initiator solution A, 1.3g Ammonium persulfate. is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 87 DEG C, add 90g monomer phase, initiator solution A is added after 1min, become after blue 15min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 162min and 160min respectively, after monomer phase and initiator solution dropwise, it is incubated 5h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Comparative example 1
The preparation of alkali-soluble acrylate's polymer: to 2L with nitrogen, agitating device four-hole boiling flask in add 1032g deionized water, 46.5gDNS-86 (allyloxy nonyl phenol propanol polyoxyethylene (10) ether ammonium sulfate), 10g triethanolamine, agitated obtain table live emulsion; In five mouthfuls of flasks with agitating device of another 2L, add 130g ethyl acrylate, 68g butyl acrylate, 50g methyl methacrylate, 40g 2-(Acryloyloxy)ethanol, 2.1g diallyl itaconate, 120g acrylic acid, 42g methacrylic acid, agitated obtain monomer phase; Ammonium persulfate. 0.12g is dissolved in 5g deionized water and obtains initiator solution A, 1.3g Ammonium persulfate. is dissolved in 68g deionized water and obtains initiator solution B;
Emulsion of being lived by table is heated to 90 DEG C, add 90g monomer phase, initiator solution A is added after 1min, become after blue 30min until aqueous phase, at the uniform velocity start at the uniform velocity dropping monomer phase after dropping initiator solution B, 2min, dropping 162min and 160min respectively, after monomer phase and initiator solution dropwise, it is incubated 3h. Resulting polymers emulsion product is cooled to room temperature, is packed by 400 order filter clothes.
Application and detection
Freeze-thaw stability method of testing: by the 100g polymer emulsion of embodiment 1～6 and comparative example 1 and commercial samples down in the transparent plastic drug package of 150gPET, plastic bottle is placed in 18h at-18 DEG C of temperature, place 25 DEG C of calorstats after frost, observe emulsion every 1h and restore situation. As emulsion breaking is layered, or have lisoloid precipitation then to judge that freeze-thaw stability is poor, as emulsion can return to original state, even if there being a little layering, but remain to return to original state after shaking up and then judge that freeze-thaw stability is good, being calculated as 1 by a freeze-thaw cycle, be calculated as 5 by five freeze-thaw cycle, total number measured is 5 circulations.
The method of testing of viscosity: using the viscosity of BrookfieldRVT viscometer determining formula, select No. 4 rotors, test rotating speed is 5rpm, after stable reading, reading is multiplied by parameter and obtains viscosity.
The method of testing of turbidity: (1) start preheating transmissometer 30min, and correct transmissometer. (2) it is encased in turbidity bottle with rustless steel medicine bale-out sample. (3) centrifugal 10min under centrifuge 1200r/m, eliminates bubble. (4) turbidity bottle equipped with sample after being centrifuged is placed at transmissometer test position, directly reads reading.
Suspendability method of testing: (1) by formulation samples down in 60mL transparent sample bottle. (2) add colored beadlet in sample bottle, be uniformly distributed to the granule of sample, bubble with spoon stirring. (3) sample bottle is placed in 40 DEG C and 48 DEG C of baking ovens observed result after 30 days: 1) if granule suspension decline 0%～5%; remember 4 points, decline 5%～30% be designated as 3 points, decline 30%～60% be designated as 2 points, decline be designated as 1 point more than 60%.
Freeze thawing test result is as shown in table 1 below:
Table 1: emulsion freeze-thaw stability test result
Application Example
According to the formula of such as table 2, the polymer emulsion of embodiment 1～6 and comparative example 1 and commercial samples is configured to transparent bath foam, and in process for preparation, formula solution becomes stirring all the time.
Table 2: the application formula of transparent bath foam
Each component (1 in process for preparation, 2,3,4) (wherein the reserved 1-2g of deionized water) in mixing container is added under agitation in proportion and sequentially, then by component 5 by formula pH furnishing about 6.5, component 6, component 7 are added, supply remaining deionized water to total amount 100%, the clear formula being configured to.
Being transferred in the transparent plastic drug package of 150gPET by clear formula after preparation, be centrifuged eliminating bubble, test its viscosity, turbidity, be eventually adding component 8 at 25 DEG C after constant temperature 24h, sample is placed in baking oven, tests suspendability.
Polymer application performance test result is as shown in table 3:
Table 3: polymer application performance test result
By embodiment, introducing due to the polymerizable bisamide surfactant of macromole, the polymer emulsion prepared can by the loop test of freeze thawing more than 5 at-18 DEG C, freeze-thaw stability is good, recovery time is short, thickening capabilities is better than the formula without bisamide, and the turbidity of formula is low, and commercially available product is unable to reach such effect.
The above-described presently preferred embodiments of the present invention that is only, all any amendment, equivalent replacement and improvement etc. made within the scope of the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a freeze-thaw stable type acrylate polymer emulsion, it is characterised in that obtained through emulsion polymerization by following components:
Unsaturated carboxylic acid monomer 6.8～14wt%;
Esters of unsaturated carboxylic acids 14～the 21.5wt% of C1-C5;
Polymerisable anionic bisamide surfactant 3～6.5wt%;
Non-polymerisable anionic surfactant 0～0.8wt%;
Initiator 0.05～0.1wt%;
Cross-linking agent 0.05～0.25wt%;
PH buffer agent 0.4～0.9wt%;
And the deionized water of surplus;
Wherein, described polymerisable anionic bisamide surfactant is below general formula:
R1Alkyl or benzene alkyl for C6～C8;
R2The alkylene containing unsaturated double-bond for C2～C5;
R3Alkylsulfonate or carboxylate for C1～C5;
N, m are 10～30.
2. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 1, it is characterised in that comprise the following steps:
Step 1: polymerisable anionic bisamide surfactant, non-polymerisable anionic surfactant, pH buffer agent are dissolved in deionized water, are warming up to 80 DEG C～90 DEG C under the protection of noble gas;
Step 2: monomer phase will be formed after the esters of unsaturated carboxylic acids of C1-C5, unsaturated carboxylic acid monomer, cross-linking agent mix homogeneously;
Step 3: preparation initiator solution;
Step 4: add the monomer phase of 19.5wt%～25wt% and the initiator of 8.5wt%～9.1wt% in the solution of step 1, start after 5min～30min to drip remaining initiator solution and remaining monomer phase, dropping 150min～200min dropwises to initiator mutually with monomer, is incubated 3h～6h.
3. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 1 and 2, it is characterized in that, described unsaturated carboxylic acid monomer is at least one in acrylic acid, methacrylic acid, itaconic acid, fumaric acid .beta.-methylacrylic acid, equisetic acid, maleic acid.
4. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 3, it is characterised in that the esters of unsaturated carboxylic acids of described C1-C5 is at least one of the Arrcostab of the C1～C5 of acrylic or methacrylic acid.
5. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 3, it is characterized in that, the esters of unsaturated carboxylic acids of described C1-C5 is the mixture of at least one and 2-(Acryloyloxy)ethanol of the Arrcostab of the C1～C5 of acrylic or methacrylic acid.
6. the preparation method of the freeze-thaw stable type acrylate polymer emulsion according to claim 4 or 5, it is characterised in that described cross-linking agent is diallyl phthalate, diallyl phthalate or diallyl itaconate.
7. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 6, it is characterised in that described initiator is Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate.
8. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 7, it is characterised in that described pH buffer agent is sodium bicarbonate, triethanolamine or triethylamine.
9. the preparation method of freeze-thaw stable type acrylate polymer emulsion according to claim 8, it is characterised in that non-polymerisable anionic surfactant is dodecylbenzene sodium sulfonate, sodium lauryl sulphate.
10. a freeze-thaw stable type acrylate polymer emulsion, it is characterised in that prepared by the method as described in as arbitrary in claim 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018086055A1 (en) * | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Aqueous coating composition |
| CN110785395A (en) * | 2017-06-26 | 2020-02-11 | 巴斯夫欧洲公司 | Alkoxylation of hydroxy acids |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103864982A (en) * | 2012-12-15 | 2014-06-18 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of fluorinated acrylate emulsion |
| CN103772625B (en) * | 2014-01-17 | 2016-03-02 | 广州市东雄化工有限公司 | A kind of frost resistance acrylate suspension thickening emulsion and preparation method thereof |
-
2016
- 2016-03-23 CN CN201610172789.8A patent/CN105669914B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103864982A (en) * | 2012-12-15 | 2014-06-18 | 东莞市长安东阳光铝业研发有限公司 | Preparation method of fluorinated acrylate emulsion |
| CN103772625B (en) * | 2014-01-17 | 2016-03-02 | 广州市东雄化工有限公司 | A kind of frost resistance acrylate suspension thickening emulsion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 袁婷婷等: "可聚合乳化剂DNS-86对丙烯酸酯乳液稳定性的影响", 《粘接》 * |
| 邓杨等: "丙烯酸酯乳液冻融稳定性的研究进展", 《材料研究与应用》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018086055A1 (en) * | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Aqueous coating composition |
| US11136465B2 (en) * | 2016-11-11 | 2021-10-05 | Dow Global Technologies Llc | Aqueous coating composition |
| CN110785395A (en) * | 2017-06-26 | 2020-02-11 | 巴斯夫欧洲公司 | Alkoxylation of hydroxy acids |
| EP3645496A1 (en) * | 2017-06-26 | 2020-05-06 | Basf Se | Alkoxylation of hydroxy acids |
| US11168048B2 (en) | 2017-06-26 | 2021-11-09 | Basf Se | Alkoxylation of hydroxy acids |
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| CN105669914B (en) | 2018-12-28 |
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