CN111187376A - Saponification-free acrylic emulsion and preparation method thereof - Google Patents
Saponification-free acrylic emulsion and preparation method thereof Download PDFInfo
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- CN111187376A CN111187376A CN202010017144.3A CN202010017144A CN111187376A CN 111187376 A CN111187376 A CN 111187376A CN 202010017144 A CN202010017144 A CN 202010017144A CN 111187376 A CN111187376 A CN 111187376A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004945 emulsification Methods 0.000 title description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- -1 acrylic acid isooctyl ester Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 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
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 14
- 239000003973 paint Substances 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 241001391944 Commicarpus scandens Species 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of polymer chemistry, in particular to a saponification-free acrylic emulsion and a preparation method thereof. The method aims to solve the problems that acrylic emulsion prepared by externally adding a small molecular emulsifier is unstable and easy to break emulsion, and a single-component paint film is not glossy due to the fact that part of the small molecular emulsifier is poor in compatibility with resin. The invention provides a saponification-free acrylic emulsion and a preparation method thereof, wherein a stable acrylic emulsion is successfully prepared by reacting a self-made prepolymer with an acrylic polymerization monomer, a neutralizer and a water-soluble initiator under the condition of not adding a small molecular emulsifier, the prepared prepolymer does not have great influence on the performances of the emulsion and a paint film, has proper viscosity, can be well mixed and dissolved with acrylic emulsion resin in water, does not generate emulsion breaking and bottom sinking, and has good application prospect.
Description
Technical Field
The invention relates to the field of polymer chemistry, in particular to a saponification-free acrylic emulsion and a preparation method thereof.
Background
Emulsification is the effect of one liquid being dispersed uniformly as very fine droplets in another liquid that is immiscible with each other. Emulsification is a liquid-liquid interface phenomenon, in which two immiscible liquids, such as oil and water, are separated into two layers in a container, with less dense oil on the upper layer and more dense water on the lower layer. If a suitable surfactant is added, the oil is dispersed in water under vigorous stirring to form an emulsion, a process called emulsification. The emulsification method is divided into an external emulsification method and a self emulsification method, wherein the external emulsification is mainly carried out by the method of adding an emulsifier, and the self emulsification is a method for emulsifying by the emulsifier, which has a hydrophilic group and a hydrophobic group.
In the conventional emulsion polymerization, the emulsion polymerization is usually carried out by emulsifying the mixture by adding an emulsifier to form an emulsion. In the external emulsification process, people usually adopt small molecular emulsifiers, such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, and anion, nonionic, cation, and nonionic combination methods to pre-emulsify the oil phase and the water phase, and the small molecular emulsifiers remain in the system and cannot be removed. And emulsion prepared by the small molecular emulsifier has poor stability to some extent, and is easy to break.
The product of the acrylic emulsion in the polymerization process is often large in molecular weight and low in solid content, and the small molecular emulsifier is remained. The micromolecular emulsifier has better hydrophilicity, and in the later paint making process, the micromolecular emulsifier remains in a paint film, so that poor water resistance of the paint film and performance defects in other aspects are easily caused. In addition, when the micromolecular emulsifier is used for emulsifying the acrylic resin with large molecular weight, the needed dosage and the emulsifying time are also longer, the emulsion prepared after emulsification is unstable and easy to break, and part of the micromolecular emulsifier has poor compatibility with the resin, so that the emulsion is unstable on one hand, and the single-component paint film is also subjected to light loss on the other hand.
In view of the above problems, there is an attempt to obtain an acrylate emulsion by an emulsion polymerization method without using an emulsifier, for example, gewanli et al, which uses ammonium persulfate as an initiator, methacrylic acid as a functional monomer, and hydroxyethyl acrylate as a crosslinking monomer to synthesize a polyacrylate soap-free emulsion adhesive for pigment dyeing, and all the fastnesses of the synthesized acrylate soap-free emulsion adhesive meet the requirements (gewanli, zhaoli, synthesis of acrylate soap-free emulsion and its application in pigment dyeing [ J, chemical and bonding, 2011,33(3):71-74.), and luxuan et al, which uses styrene, butyl acrylate, acrylic acid, and a colloid protector to prepare a stable and excellent-performance acrylic resin emulsion adhesive by a soap-free seed emulsion polymerization method. The acrylic resin emulsion is used as a main agent, silica sol and blocked isocyanate are used as an additional cross-linking agent to prepare the formaldehyde-free artificial board adhesive N-hydroxymethyl acrylamide with excellent performance as a monomer, polyvinyl alcohol (PVA) is used as a protective colloid, and a soap-free seed emulsion polymerization method is adopted to prepare the stable acrylic resin emulsion adhesive with excellent performance. The acrylic resin emulsion is used as a main agent, and silica sol and blocked isocyanate are used as an additional cross-linking agent to prepare the formaldehyde-free artificial board adhesive with excellent performance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the acrylic emulsion prepared by adding the micromolecular emulsifier is unstable and easy to break emulsion, and part of the micromolecular emulsifier has poor compatibility with resin, so that the emulsion is unstable and a single-component paint film is also subjected to light loss. The invention provides a saponification-free acrylic emulsion, which is prepared by successfully reacting a self-made prepolymer with an acrylic acid polymerization monomer, a neutralizer and a water-soluble initiator under the condition of not adding a small molecular emulsifier, wherein the prepolymer is prepared by selecting a tertiary carboxylic acid glycidyl ester (E10P) monomer, because E10P has larger steric hindrance and has excellent viscosity reducing effect, the molecular weight of the whole prepolymer can be controlled, the molecular weight of the prepolymer is not suitable to be too large, and the use of an organic solvent is avoided by taking E10P as a reaction medium, so that the 0VOC of the reaction is realized. Too much addition of E10P results in the consumption of a large amount of acrylic acid, on the one hand, leading to a reduction or even the absence of other acrylic monomers, and too little addition results in a lower acid value of the overall emulsifier, failing to achieve the desired acid value and emulsifying effect.
Because E10P is used for being the primer solvent, realizes bulk polymerization, is the key of reducing solvent content, if E10P addition is low excessively, can lead to the primer material on the one hand less, unable synthetic operation, or need introduce partial solvent and can enter the operation, can increase VOC content, on the other hand add excessively, lead to whole viscosity bigger, unable operation, difficult ejection of compact. The molecular weight of the prepolymer is controlled to be 6000-8000g/mol, and compared with an additional micromolecule emulsifier, the prepolymer prepared by the method does not have great influence on the performances of the emulsion and a paint film, and has proper viscosity. In addition, the acid value of the prepolymer is controlled to be about 200mg KOH/g, on one hand, through organic amine neutralization, hydrophilic groups are introduced to form ammonium ions, one end of the ammonium ions is hydrophilic, the other end of the ammonium ions is hydrophobic, the ammonium ions have a good emulsifying effect on monomers, the ammonium ions are suitable for an oil-in-water system, the prepared emulsion is more stable, on the other hand, the prepolymer has a good hydrophilic effect, and in addition, the structure of the prepolymer and the structure of emulsion resin are similar, so that the prepolymer can be well mixed and dissolved with acrylic emulsion resin in water, and emulsion breaking and bottom sinking cannot occur.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a saponification-free acrylic emulsion which is characterized by comprising the following components in percentage by mass, wherein the total content of all the components is 100 percent:
specifically, the molecular weight of the prepolymer is 4000-6000g/mol, and the acid value is 180-200mg KOH/g.
Specifically, the prepolymer comprises the following components:
E10P
acrylic acid isooctyl ester
Styrene (meth) acrylic acid ester
Methacrylic acid methyl ester
Acrylic acid
Di-tert-amyl peroxide
Dimethylethanolamine
Deionized water
Specifically, the prepolymer is prepared according to the following steps:
(1) weighing 7g E10P, adding the weighed materials into a four-neck flask with condensation, and heating to 150-155 ℃;
(2) quantitatively weighing 5.7g of isooctyl acrylate, 11.58g of styrene, 2.2g of methyl methacrylate, 12.12g of acrylic acid and 1.4g of di-tert-amyl peroxide, and uniformly mixing for later use;
(3) when the temperature in the step (1) is raised to 150-155 ℃, dropwise adding the mixed solution in the step (2) into E10P within 4-5h, and monitoring the temperature and the acid value; and after the dropwise addition is finished, 0.12g of di-tert-amyl peroxide is added, the temperature is kept for 2 hours at the temperature of 155 ℃ plus materials, after the temperature is kept for 2 hours, the temperature is reduced to 80-90 ℃, 9.56g of dimethylethanolamine is added, and the mixture is stirred by adding water until the product has a flowing state, so that the prepolymer is obtained.
Specifically, the water-soluble initiator is a water-soluble initiator capable of free radical polymerization.
Specifically, the water-soluble initiator is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
A preparation method of a nonsaponifiable acrylic emulsion comprises the following steps:
(1) dissolving a water-soluble initiator in deionized water, wherein the weight of the deionized water accounts for 3% of the total mass of the whole formula for later use;
(2) uniformly mixing styrene, acrylic acid, butyl acrylate, hydroxyethyl methacrylate and methyl methacrylate, adding the prepolymer, stirring at a high speed for 1.5h, adding the water-soluble initiator aqueous solution obtained in the step (1) accounting for 3.5% of the total mass of the whole formula, and uniformly mixing;
(3) putting the rest deionized water into a four-neck flask, heating to 80 ℃, adding the mixed solution obtained in the step (2), stirring to be transparent, and dropwise adding the mixed solution obtained in the step (2) into the 80 ℃ deionized water within 5-6 h;
(4) and (4) after the mixed solution obtained in the step (3) is dripped, adding the water-soluble initiator aqueous solution remained in the step (1), preserving heat for 2 hours, cooling and discharging.
The invention has the beneficial effects that:
(1) the nonsaponifiable acrylic emulsion prepared by the invention has no external emulsifier, does not influence the performances of a paint film and resin, and has better water resistance and paint film glossiness;
(2) the nonsaponifiable acrylic emulsion prepared by the invention has excellent emulsification effect and is more stable;
(3) the nonsaponifiable acrylic emulsion prepared by the invention has higher solid content and lower viscosity;
(4) the method for preparing the saponification-free acrylic emulsion is more environment-friendly, and has high economic value, low cost and strong operability;
(5) the emulsifier-free acrylic emulsion prepared by the invention has no external emulsifier, does not need to remove the emulsifier, and does not have the problem of poor compatibility.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Examples
Preparation of prepolymer
(1) Weighing 7g E10P, adding the weighed materials into a four-neck flask with condensation, and heating to 150-155 ℃;
(2) quantitatively weighing 5.7g of isooctyl acrylate, 11.58g of styrene, 2.2g of methyl methacrylate, 12.12g of acrylic acid and 1.4g of di-tert-amyl peroxide, and uniformly mixing for later use;
(3) when the temperature in the step (1) is raised to 150-155 ℃, dropwise adding the mixed solution in the step (2) into E10P within 4-5h, and monitoring the temperature and the acid value; and after the dropwise addition is finished, 0.12g of di-tert-amyl peroxide is added, the temperature is kept for 2 hours at the temperature of 155 ℃ plus materials, after the temperature is kept for 2 hours, the temperature is reduced to 80-90 ℃, 9.56g of dimethylethanolamine is added, and the mixture is stirred by adding water until the product has a flowing state, so that the prepolymer is obtained.
(II) preparation of nonsaponifiable acrylic emulsion
(1) Dissolving a water-soluble initiator in deionized water, wherein the weight of the deionized water accounts for 3% of the total mass of the whole formula for later use;
(2) uniformly mixing styrene, acrylic acid, butyl acrylate, hydroxyethyl methacrylate and methyl methacrylate, adding the prepolymer, stirring at a high speed for 1.5h, adding the water-soluble initiator aqueous solution obtained in the step (1) accounting for 3.5% of the total mass of the whole formula, and uniformly mixing;
(3) putting the rest deionized water into a four-neck flask, heating to 80 ℃, adding the mixed solution obtained in the step (2), stirring to be transparent, and dropwise adding the mixed solution obtained in the step (2) into the 80 ℃ deionized water within 5-6 h;
(4) and (4) after the mixed solution obtained in the step (3) is dripped, adding the water-soluble initiator aqueous solution remained in the step (1), preserving heat for 2 hours, cooling and discharging.
The components of examples 1 to 3 and comparative examples 1 to 2 prepared according to the above-described method are shown in the following table 1:
TABLE 1
Comparative examples 3 to 5 are the same as example 3 except that, as shown in Table 2:
TABLE 2
The performance of the nonsaponifiable acrylic emulsions prepared in examples 1 to 3 and comparative examples 1 to 5 was tested and shown in tables 3 and 4: TABLE 3
| Examples | Emulsion state | Solid content (%) | Stability (50 ℃/14d) | Slag formation rate |
| Example 1 | Transparent state | 43.55 | By passing | 2‰ |
| Example 2 | Transparent state | 47.52 | By passing | 6‰ |
| Example 3 | Transparent state | 46.43 | By passing | 3‰ |
| Comparative example 1 | Transparent state | 40.42 | Failed through | 2‰ |
| Comparative example 2 | Milky white color | 46.05 | Failed through | 15‰ |
TABLE 4
As can be seen from the above-mentioned studies of examples 1-3 and comparative examples 1-5, the method of the present invention can successfully prepare the nonsaponifiable acrylic emulsion, the scheme of example 3 has the advantage that the heat storage performance of comparative example 1 is not stabilized mainly by adding too little emulsifier, while the acrylic emulsion of comparative example 2 is stabilized mainly by excessive hydrophilic groups, resulting in more polymerization in the water phase and slagging. In addition, as compared with the acrylic emulsion prepared by adding the small molecular emulsifier (namely, comparative examples 3-5), the nonsaponifiable acrylic emulsion prepared by the invention has more obvious advantages in all aspects of performances than the acrylic emulsion prepared by adding the small molecular emulsifier.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. The nonsaponifiable acrylic emulsion is characterized by comprising the following components in percentage by mass, wherein the total content of all the components is 100 percent:
prepolymer 2.5-4%
14 to 15 percent of styrene
Acrylic acid 0.89-1%
8.5 to 10.5 percent of butyl acrylate
13-15% of methyl methacrylate
4.5 to 4.8 percent of hydroxyethyl methacrylate
0.18 to 0.22 percent of water-soluble initiator
The balance of deionized water.
2. The nonsaponifiable acrylic emulsion of claim 1 wherein: the molecular weight of the prepolymer is 4000-6000g/mol, and the acid value is 180-200mg KOH/g.
3. The nonsaponifiable acrylic emulsion of claim 1, wherein the prepolymer comprises the following components:
E10P
acrylic acid isooctyl ester
Styrene (meth) acrylic acid ester
Methacrylic acid methyl ester
Acrylic acid
Di-tert-amyl peroxide
Dimethylethanolamine
Deionized water.
4. The soap-free acrylic emulsion of claim 1, wherein the prepolymer is prepared by the steps of:
(1) weighing 7g E10P, adding the weighed materials into a four-neck flask with condensation, and heating to 150-155 ℃;
(2) quantitatively weighing 5.7g of isooctyl acrylate, 11.58g of styrene, 2.2g of methyl methacrylate, 12.12g of acrylic acid and 1.4g of di-tert-amyl peroxide, and uniformly mixing for later use;
(3) when the temperature in the step (1) is raised to 150-155 ℃, dropwise adding the mixed solution in the step (2) into E10P within 4-5h, and monitoring the temperature and the acid value; and after the dropwise addition is finished, 0.12g of di-tert-amyl peroxide is added, the temperature is kept for 2 hours at the temperature of 155 ℃ plus materials, after the temperature is kept for 2 hours, the temperature is reduced to 80-90 ℃, 9.56g of dimethylethanolamine is added, and the mixture is stirred by adding water until the product has a flowing state, so that the prepolymer is obtained.
5. The nonsaponifiable acrylic emulsion of claim 1 wherein: the water-soluble initiator is a water-soluble initiator capable of free radical polymerization.
6. The nonsaponifiable acrylic emulsion of claim 1 wherein: the water-soluble initiator is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
7. The preparation method of the nonsaponifiable acrylic emulsion is characterized by comprising the following steps:
(1) dissolving a water-soluble initiator in deionized water, wherein the weight of the deionized water accounts for 3% of the total mass of the whole formula for later use;
(2) uniformly mixing styrene, acrylic acid, butyl acrylate, hydroxyethyl methacrylate and methyl methacrylate, adding the prepolymer, stirring at a high speed for 1.5h, adding the water-soluble initiator aqueous solution obtained in the step (1) accounting for 3.5% of the total mass of the whole formula, and uniformly mixing;
(3) putting the rest deionized water into a four-neck flask, heating to 80 ℃, adding the mixed solution obtained in the step (2), stirring to be transparent, and dropwise adding the mixed solution obtained in the step (2) into the 80 ℃ deionized water within 5-6 h;
(4) and (4) after the mixed solution obtained in the step (3) is dripped, adding the water-soluble initiator aqueous solution remained in the step (1), preserving heat for 2 hours, cooling and discharging.
Priority Applications (1)
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Cited By (2)
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| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN113929811A (en) * | 2021-10-18 | 2022-01-14 | 杭州传化精细化工有限公司 | In-situ self-crosslinking acrylate miniemulsion and preparation method thereof |
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| CN112279967A (en) * | 2020-10-29 | 2021-01-29 | 广东衡光新材料科技有限公司 | Preparation method of oleic acid modified soap-free acrylic emulsion |
| CN113929811A (en) * | 2021-10-18 | 2022-01-14 | 杭州传化精细化工有限公司 | In-situ self-crosslinking acrylate miniemulsion and preparation method thereof |
| CN113929811B (en) * | 2021-10-18 | 2023-02-14 | 杭州传化精细化工有限公司 | In-situ self-crosslinking acrylate miniemulsion and preparation method thereof |
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| CN111187376B (en) | 2021-11-02 |
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