CN113980168A - Preparation method of gradient core-shell acrylic emulsion for outdoor wood paint - Google Patents
Preparation method of gradient core-shell acrylic emulsion for outdoor wood paint Download PDFInfo
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- CN113980168A CN113980168A CN202111259035.3A CN202111259035A CN113980168A CN 113980168 A CN113980168 A CN 113980168A CN 202111259035 A CN202111259035 A CN 202111259035A CN 113980168 A CN113980168 A CN 113980168A
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- 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
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
Abstract
The invention provides a preparation method of a gradient core-shell acrylic emulsion for outdoor wood paint, which relates to the technical field of high polymer materials, and comprises the following steps: (1) preparing a pre-emulsion A; (2) preparing a pre-emulsion B; (3) preparing an initiator solution; (4) preparing a seed emulsion; (5) and (3) monomer polymerization: putting the seed emulsion into a reaction kettle, dropping the pre-emulsion A into the residual pre-emulsion B, simultaneously dropping the mixed solution of the pre-emulsion A and the pre-emulsion B and the initiator solution into the reaction kettle synchronously for polymerization, and keeping constant-speed dropping in the dropping process and keeping the synchronous dropping completion of the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution; stirring is kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature of the reaction kettle is kept constant between 84 and 86 ℃ for 60 min; (6) then eliminating, neutralizing and discharging.
Description
Technical Field
The invention relates to the technical field of preparation methods of high polymer materials, in particular to a preparation method of a gradient core-shell acrylic emulsion for outdoor wood paint.
Background
Outdoor wood is easy to go moldy, change color, deform, deteriorate and the like due to long-term natural conditions such as wind blowing, sunshine, rain and the like, and therefore outdoor wood lacquer needs to be coated for protection. The water-based wood paint is more and more favored by people due to the outstanding environmental protection performance, and the main performance of the outdoor water-based wood paint needs to have certain water resistance, weather resistance, flexibility and the like. The acrylic emulsion has the characteristics of light and color retention, flexible formula adjustment, lower price and the like, and is used as main resin in the water-based wood lacquer.
The applicant has found that the prior art has at least the following technical problems: the acrylic emulsion polymerization process commonly used at present mainly comprises the following steps: an intermittent emulsion polymerization process, a semi-continuous emulsion polymerization process, a pre-emulsification emulsion polymerization process, a seed emulsion polymerization process, and a core-shell emulsion polymerization process. However, the conventional emulsion polymerization has the problems that the copolymerization composition of the polymer is not uniform, and the emulsion particle structure is diversified, so that the current acrylic emulsion has certain limitations on water resistance and weather resistance.
Disclosure of Invention
The invention aims to provide a preparation method of a gradient core-shell acrylic emulsion for outdoor wood lacquer, wherein emulsion particles of the acrylic emulsion prepared by the invention are gradient core-shell emulsion particles, also called multilayer structure emulsion particles, and have emulsion particles with a structure like onion, and in the polymerization process, the mass ratio of core monomers and shell monomers added into a reaction kettle is changed in a regular increasing or decreasing manner continuously, so that the composition structure of the emulsion particles is also changed in a regular increasing or decreasing manner from inside to outside. The emulsion particles of the acrylic emulsion are of a soft core and hard shell structure, the soft core endows the emulsion particles with flexibility, the hard shell endows the emulsion particles with durability, and the multilayer core-shell structure has a wider glass transition temperature, so that the problem of no stickiness during low-temperature film forming can be solved. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a gradient core-shell acrylic emulsion for outdoor wood paint, which comprises the following steps:
(1) preparation of pre-emulsion a: firstly, dissolving an emulsifier in deionized water, sequentially adding acrylate monomers at a certain stirring speed, wherein the acrylate monomers comprise cross-linking monomers, functional monomers, hard monomers and soft monomers of acrylate, and continuously stirring for 30min to obtain milky white liquid;
(2) preparation of pre-emulsion B: firstly, dissolving an emulsifier in deionized water, sequentially adding acrylate monomers at a certain stirring speed, wherein the acrylate monomers comprise acrylate functional monomers, soft monomers and hard monomers, and continuously stirring for 30min to obtain milky white liquid;
(3) preparing an initiator solution: dissolving an initiator in deionized water to obtain an initiator solution;
(4) preparing a seed emulsion: dissolving an emulsifier in deionized water, starting stirring, heating to 79-81 ℃, adding a certain amount of pre-emulsion B, adding a certain amount of initiator solution after the temperature is stable, heating to 84-86 ℃ for 30min after the emulsion is initiated to show obvious blue light, and obtaining seed emulsion;
(5) and (3) monomer polymerization: putting the seed emulsion into a reaction kettle, dropwise adding the pre-emulsion A into the rest pre-emulsion B, synchronously dropwise adding the mixed solution formed by the pre-emulsion A and the pre-emulsion B and the initiator solution into the reaction kettle for polymerization, and dropwise adding at a constant speed in the dropwise adding process and synchronously dropwise adding the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution; stirring is kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature of the reaction kettle is kept constant between 84 and 86 ℃ for 60 min;
(6) then eliminating, neutralizing and discharging.
According to a preferred embodiment, in the step (1), the amount of the emulsifier is 1 to 1.5% of the total amount of the monomers; the dosage of the acrylate monomer is 40-60% of the total amount of the monomer, and the emulsifier comprises one or more of an anionic emulsifier, an anionic non-composite emulsifier and a reactive emulsifier; the crosslinking monomer comprises DAAM or AAEM; the functional monomer comprises acrylic acid or methacrylic acid; the hard monomer comprises one or two of methyl methacrylate and styrene; the soft monomer comprises one or two of butyl acrylate and isooctyl acrylate. Preferably, in step (1), the amount of the hard monomer is larger than the amount of the soft monomer.
According to a preferred embodiment, in the step (2), the amount of the emulsifier is 1 to 1.5% of the total amount of the monomers; the dosage of the acrylate monomer is 40-60% of the total amount of the monomer, and the emulsifier comprises one or more of an anionic emulsifier, an anionic non-composite emulsifier and a reactive emulsifier; the hard monomer comprises one or two of methyl methacrylate and styrene; the soft monomer comprises one or two of butyl acrylate and isooctyl acrylate; the functional monomer includes acrylic acid or methacrylic acid. Preferably, in step (2), the amount of soft monomer is greater than the amount of hard monomer.
According to a preferable embodiment, in the step (3), the initiator is a thermal initiator, the initiator comprises one of ammonium persulfate, sodium persulfate or potassium persulfate, the amount of the initiator is 0.25-0.35% of the total amount of the monomers, and the amount of deionized water is 50-60 times diluted by the amount of the initiator.
According to a preferred embodiment, in step (4), the amount of the pre-emulsion B added is 3 to 5% of the total amount of the pre-emulsion B prepared in step (2); the amount of the added initiator solution is 1/5-1/3 of the total amount of the initiator solution prepared in the step (3).
According to a preferred embodiment, in the step (5), a dropping pump is adopted to accurately control the dropping speed, and the dropping time is controlled to be 230-240 min.
According to a preferred embodiment, the post-elimination step comprises cooling the monomer-polymerized material to 63-65 ℃, adding a certain amount of oxidant and reducer, and keeping the temperature at 65 ℃ for 30 min; wherein the oxidizing agent comprises tert-butyl hydroperoxide, and the reducing agent comprises one of ascorbic acid, sodium formaldehyde sulfoxylate or FF 6M.
According to a preferred embodiment, the amount of the oxidant is 0.1 to 0.2% of the total amount of the monomers, and the amount of the reducing agent is 0.05 to 0.1% of the total amount of the monomers.
According to a preferred embodiment, the neutralization step comprises cooling to below 50 ℃ after the post-elimination step, adding a certain amount of neutralizing agent, and controlling the pH value to 7.5-8.5 after the dripping is finished; the neutralizing agent comprises one of ammonia water, diethanol amine, triethanolamine or AMP-95.
According to a preferred embodiment, the discharging step comprises, after the neutralization step, reducing the temperature to below 40 ℃, adding a certain amount of bactericide, stirring for 30min, filtering the discharged material; the amount of the bactericide is 0.01-0.02% of the total amount of the system, and the bactericide comprises isothiazolinone compounds.
Based on the technical scheme, the preparation method of the gradient core-shell acrylic emulsion for the outdoor wood lacquer at least has the following technical effects:
the preparation method adopts a 'gradient feeding' emulsion polymerization method, the emulsion particles of the prepared acrylic emulsion are gradient core-shell emulsion particles, also called multilayer structure emulsion particles, and have emulsion particles with an onion structure, as shown in figure 2, in the polymerization process, the mass ratio of the core monomer and the shell monomer added into a reaction kettle is changed in a regular increasing or decreasing manner, so that the composition structure of the emulsion particles is also changed in a regular increasing or decreasing manner from inside to outside. The emulsion particles of the acrylic emulsion are of a soft core and hard shell structure, wherein the soft core is from pre-emulsion B, the total Tg of the monomers is less than 0 ℃, the hard shell is from pre-emulsion A, the total Tg of the monomers is greater than 80 ℃, the emulsion particles gradually transition from the pre-emulsion B to the pre-emulsion A from inside to outside along with the progress of the polymerization process, and compared with the prior art that a continuous phase shell layer is soft and easy to stick after the film formation of the hard core and soft shell particles, the continuous phase of the soft core and hard shell particles is hard and not easy to stick after the film formation, the particles do not have phase separation, and the durability is better. The soft core endows the soft core, the hard shell endows the hard core with durability, and the multilayer core-shell structure has a wider glass transition temperature, so that the problem of no stickiness during low-temperature film forming can be solved. The latex paint film prepared from the emulsion has good flexibility, good water resistance, chemical resistance and stain resistance, and the QUV resistance can reach 2000h, and can meet the main performance of outdoor wood paint.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a gradient core-shell acrylic emulsion according to the present invention;
FIG. 2 is a schematic structural diagram of the latex particles prepared by the preparation method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The raw materials and their mass ratios required in example 1 are shown in table 1 below:
TABLE 1 raw materials and mass ratios required for example 1
| Raw materials | Mass ratio/%) |
| Water (W) | 57～62 |
| Sodium dodecyl sulfate K12 | 0.8～1 |
| Methacrylic acid methyl ester | 25～26 |
| Acrylic acid butyl ester | 12～13 |
| Acrylic acid | 1～2 |
| Diacetone acrylamide | 0.7～0.9 |
| Adipic acid dihydrazide | 0.35～0.45 |
| Ammonium persulfate | 0.08～0.10 |
| Tert-butyl hydroperoxide | 0.02～0.04 |
| Hanging white block | 0.02～0.04 |
| 20% ammonia water | 0.6～0.8 |
| Bactericide | 0.01～0.02 |
The acrylic emulsion of example 1 was prepared as follows:
(1) preparation of pre-emulsion a: dissolving 1/4 parts of 0.8-1 part of emulsifier K12 in 4/15 parts of 57-62 parts of deionized water, sequentially adding 0.4-0.5 part of acrylic acid, 1-2 parts of butyl acrylate and 17-19 parts of methyl methacrylate at a certain stirring speed, and continuously stirring for 30min to obtain milky liquid for later use;
(2) preparation of pre-emulsion B: dissolving 1/4 parts of 0.8-1 part of emulsifier K12 in 4/15 parts of 57-62 parts of deionized water, adding 0.7-0.9 part of diacetone acrylamide under a certain stirring speed, sequentially adding 0.4-0.5 part of acrylic acid, 10-12 parts of butyl acrylate and 7-8 parts of methyl methacrylate after the diacetone acrylamide is completely dissolved, and continuously stirring for 30min to obtain a milky liquid for later use;
(3) preparation of initiator solution: dissolving 0.08-0.10 part of ammonium persulfate in 57-62 parts of deionized water to obtain an initiator solution for later use;
(4) preparing a seed emulsion: dissolving 1/2 parts of emulsifier K12 in an amount of 57-62 parts of deionized water in an amount of 1/3 parts, stirring, heating to 79-81 ℃, adding 3-5% of pre-emulsion BB, adding 1/5 parts of initiator solution after the temperature is stable, initiating until the emulsion shows obvious blue light, and keeping the temperature at 84-86 ℃ for 30min to obtain seed emulsion for later use;
(5) and (3) monomer polymerization: the method comprises the following steps of dropwise adding a pre-emulsion A into a pre-emulsion B, dropwise adding a mixed solution of the pre-emulsion A and the pre-emulsion B and an initiator solution into a seed emulsion in a reaction kettle, ensuring that the pre-emulsion A, the pre-emulsion B and the initiator solution are dropwise added simultaneously, controlling the dropping speed to be dropped within 230-240 min, keeping the dropping process at a constant speed, and enabling the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution to be dropped simultaneously. That is, as shown in fig. 1, the pre-emulsion a is dropped into the pre-emulsion B, the mixture of the pre-emulsion a and the pre-emulsion B is dropped into the reaction kettle, and the initiator solution is dropped into the reaction kettle; stirring is always kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature is kept constant between 84 and 86 ℃ for 60 min;
(6) post-elimination: cooling to 63-65 ℃, sequentially adding 0.02-0.04 part of tert-butyl hydroperoxide and 0.02-0.04 part of sodium formaldehyde sulfoxylate, and preserving heat at 65 ℃ for 30 min;
(7) neutralizing: cooling to below 50 ℃, adding a certain amount of ammonia water, and controlling the pH value to 7.5-8.5 after the addition is finished;
(8) discharging: and (3) cooling the temperature to below 40 ℃, adding 0.01-0.02 part of bactericide, stirring for 30min, filtering and discharging.
Example 2
The raw materials and their mass ratios required in example 2 are as follows:
TABLE 2 raw materials and mass ratios required for example 2
The acrylic emulsion of example 2 was prepared as follows:
(1) preparation of pre-emulsion a: firstly, 0.8-1 part of 1/4 amount of an emulsifier SR1025 is dissolved in 4/15 amount of 57-62 parts of deionized water, 0.4-0.5 part of methacrylic acid, 1-2 parts of butyl acrylate, 11-15 parts of methyl methacrylate and 4-6 parts of styrene are sequentially added under a certain stirring rotating speed, and stirring is continuously carried out for 30min to obtain milky liquid for later use;
(2) preparation of pre-emulsion B: firstly, 0.8-1 part of 1/4 amount of an emulsifier SR1025 is dissolved in 4/15 amount of 57-62 parts of deionized water, 0.7-0.9 part of diacetone acrylamide is added under a certain stirring speed, after the diacetone acrylamide is completely dissolved, 0.4-0.5 part of methacrylic acid, 10-12 parts of butyl acrylate and 7-8 parts of methyl methacrylate are sequentially added, and stirring is continuously carried out for 30min to obtain milky liquid for later use;
(3) preparation of initiator solution: dissolving 0.08-0.10 part of potassium persulfate in 57-62 parts of deionized water to obtain an initiator solution for later use;
(4) preparing a seed emulsion: dissolving 1/2 weight parts of 0.8-1 weight part of emulsifier SR-1025 into 1/3 weight parts of 57-62 weight parts of deionized water, starting stirring, heating to 79-81 ℃, adding 3-5% of monomer pre-emulsion B, adding 1/5 weight parts of total amount of initiator solution after the temperature is stabilized, initiating until the emulsion shows obvious blue light, and keeping the temperature at 84-86 ℃ for 30min to obtain seed emulsion for later use;
(5) and (3) monomer polymerization: dropwise adding the pre-emulsion A into the pre-emulsion B, and simultaneously dropwise adding the mixed solution of the pre-emulsion A and the pre-emulsion B and the initiator solution into the seed emulsion in the reaction kettle, so as to ensure that the pre-emulsion A, the pre-emulsion B and the initiator solution start to be dropwise added simultaneously, the dropping speed is controlled to be completed within 230-240 min, the dropwise adding process is kept at a constant speed, and the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution are completely dropwise added simultaneously; that is, as shown in fig. 1, the pre-emulsion a is dropped into the pre-emulsion B, the mixture of the pre-emulsion a and the pre-emulsion B is dropped into the reaction kettle, and the initiator solution is dropped into the reaction kettle; stirring is always kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature is kept constant between 84 and 86 ℃ for 60 min;
(6) post-elimination: cooling to 63-65 ℃, sequentially adding 0.02-0.04 part of tert-butyl hydroperoxide and 0.02-0.04 part of sodium formaldehyde sulfoxylate, and preserving heat at 65 ℃ for 30 min;
(7) neutralizing: cooling to below 50 ℃, adding a certain amount of ammonia water, and controlling the pH value to 7.5-8.5 after the addition is finished;
(8) discharging: and (3) cooling the temperature to below 40 ℃, adding 0.01-0.02 part of bactericide, stirring for 30min, filtering and discharging.
Example 3
The raw materials and their mass ratios required in example 3 are as follows:
TABLE 3 raw materials and mass ratios required for example 3
| Raw materials | Mass ratio/%) |
| Water (W) | 57-62 |
| Dodecadiphenyloxide disulfonic acid sodium salt DOWFAX2A1 | 0.8-1 |
| Methacrylic acid methyl ester | 20-21 |
| Styrene (meth) acrylic acid ester | 4-6 |
| Acrylic acid isooctyl ester | 12-13 |
| Acrylic acid | 1-2 |
| Diacetone acrylamide | 0.7-0.9 |
| Adipic acid dihydrazide | 0.35-0.45 |
| Sodium persulfate | 0.08-0.10 |
| Tert-butyl hydroperoxide | 0.02-0.04 |
| Hanging white block | 0.02-0.04 |
| AMP-95 | 0.5-0.7 |
| Bactericide | 0.01-0.02 |
The acrylic emulsion of example 3 was prepared as follows:
(1) preparation of pre-emulsion a: dissolving 1/4 parts of 0.8-1 part of emulsifier 2A1 in 4/15 parts of 57-62 parts of deionized water, sequentially adding 0.4-0.5 part of acrylic acid, 1-2 parts of isooctyl acrylate, 11-15 parts of methyl methacrylate and 4-6 parts of styrene at a certain stirring speed, and continuously stirring for 30min to obtain milky liquid for later use;
(2) preparation of pre-emulsion B: dissolving 1/4 parts of 0.8-1 part of emulsifier 2A1 in 4/15 parts of 57-62 parts of deionized water, adding 0.7-0.9 part of diacetone acrylamide under certain stirring speed, sequentially adding 0.4-0.5 part of acrylic acid, 10-12 parts of isooctyl acrylate and 7-8 parts of methyl methacrylate after the diacetone acrylamide is completely dissolved, and continuously stirring for 30min to obtain milky liquid for later use;
(3) preparation of initiator solution: dissolving 0.08-0.10 part of sodium persulfate in 57-62 parts of deionized water to obtain an initiator solution for later use;
(4) preparing a seed emulsion: dissolving 1/2 parts of emulsifier 2A1 in 0.8-1 part of emulsifier 2A1 in 1/3 parts of deionized water in 57-62 parts of deionized water, starting stirring, heating to 79-81 ℃, adding 3% -5% of pre-emulsion B, adding 1/5 parts of initiator solution after the temperature is stabilized, initiating until the emulsion shows obvious blue light, and keeping the temperature at 84-86 ℃ for 30min to obtain seed emulsion for later use;
(5) and (3) monomer polymerization: dropwise adding the pre-emulsion A into the pre-emulsion B, and simultaneously dropwise adding the mixed solution of the pre-emulsion A and the pre-emulsion B and the initiator solution into the seed emulsion in the reaction kettle, so as to ensure that the pre-emulsion A, the pre-emulsion B and the initiator solution start to be dropwise added simultaneously, the dropping speed is controlled to be completed within 230-240 min, the dropwise adding process is kept at a constant speed, and the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution are completely dropwise added simultaneously; that is, as shown in fig. 1, the pre-emulsion a is dropped into the pre-emulsion B, the mixture of the pre-emulsion a and the pre-emulsion B is dropped into the reaction kettle, and the initiator solution is dropped into the reaction kettle; stirring is always kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature is kept constant between 84 and 86 ℃ for 60 min;
(6) post-elimination: cooling to 63-65 ℃, sequentially adding 0.02-0.04 part of tert-butyl hydroperoxide and 0.02-0.04 part of sodium formaldehyde sulfoxylate, and keeping the temperature at 65 ℃ for 30 min;
(7) neutralizing: cooling to below 50 deg.C, adding a certain amount of AMP-95, and controlling pH to 7.5-8.5;
(8) discharging: cooling to below 40 deg.C, adding 0.01-0.02 part of bactericide, stirring for 30min, filtering, and discharging.
Example 4
The emulsions prepared in examples 1 to 3 were each formulated as a white paint, the parameter formulation of which is given in table 4 below:
TABLE 4 raw material composition and mass ratio of white paint
| Number of component | Raw material components | Mass ratio/%) |
| 1 | Water (W) | 7 |
| 2 | BYK190 | 0.4 |
| 3 | Titanium white R-706 | 18 |
| 4 | Emulsion and method of making | 60 |
| 5 | AMP-95 | 0.1 |
| 6 | TEGO810 | 0.1 |
| 7 | BYK346 | 0.3 |
| 8 | BYK024 | 0.2 |
| 9 | DPM | 3 |
| 10 | DPnB | 4 |
| 11 | Water (W) | 0.4 |
| 12 | RM-8W | 0.4 |
| 13 | BYK539 | 3 |
| 14 | RM-2020 | 0.3 |
| 15 | GRACESY-7000 | 2.5 |
| 16 | TEGO902W | 0.3 |
| Total up to | 100 |
The preparation method comprises the following steps: taking a proper dispersion cylinder, adding the raw material components with the serial numbers 1 and 2, starting a dispersion machine, and rotating at 800-1000 rpm; slowly adding the raw material components of the serial number 3 under stirring, and dispersing for 20-25 min by adjusting the rotation speed to 1500 rpm; reducing the rotating speed to 800-1000 rpm, sequentially and slowly adding the raw material components with the serial numbers of 4-16, dispersing for 20-25 min, filtering by a 200-mesh filter screen, and discharging.
Table 5 shows the results of the application performance tests carried out on the white paints formulated with the emulsions of examples 1 to 3, the results being as follows:
TABLE 5 application Performance test results
From the results, the white paint prepared from the emulsion has good flexibility, good water resistance, chemical resistance and stain resistance, and can meet the main performances of outdoor wood paint.
In addition, the equipment required by the invention is basically consistent with the conventional core-shell emulsion polymerization, and two pre-emulsification kettles, one initiator kettle, one reaction kettle and three dropping pumps are required to be arranged. Three dripping pumps are required to work synchronously, the dripping speed is easy to control, the pre-emulsification kettle and the reaction kettle are always stirred in the dripping process, and the temperature is kept constant.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A preparation method of a gradient core-shell acrylic emulsion for outdoor wood paint is characterized by comprising the following steps:
(1) preparation of pre-emulsion a: firstly, dissolving an emulsifier in deionized water, sequentially adding acrylate monomers at a certain stirring speed, wherein the acrylate monomers comprise cross-linking monomers, functional monomers, hard monomers and soft monomers of acrylate, and continuously stirring for 30min to obtain milky white liquid;
(2) preparation of pre-emulsion B: firstly, dissolving an emulsifier in deionized water, sequentially adding acrylate monomers at a certain stirring speed, wherein the acrylate monomers comprise acrylate functional monomers, soft monomers and hard monomers, and continuously stirring for 30min to obtain milky white liquid;
(3) preparing an initiator solution: dissolving an initiator in deionized water to obtain an initiator solution;
(4) preparing a seed emulsion: dissolving an emulsifier in deionized water, starting stirring, heating to 79-81 ℃, adding a certain amount of pre-emulsion B, adding a certain amount of initiator solution after the temperature is stable, heating to 84-86 ℃ for 30min after the emulsion is initiated to show obvious blue light, and obtaining seed emulsion;
(5) and (3) monomer polymerization: putting the seed emulsion into a reaction kettle, dropwise adding the pre-emulsion A into the rest pre-emulsion B, synchronously dropwise adding the mixed solution formed by the pre-emulsion A and the pre-emulsion B and the initiator solution into the reaction kettle for polymerization, and dropwise adding at a constant speed in the dropwise adding process and synchronously dropwise adding the mixed solution of the pre-emulsion A, the pre-emulsion A and the pre-emulsion B and the initiator solution; stirring is kept during the dripping process, the temperature of the reaction kettle is kept between 84 and 86 ℃, and after the dripping is finished, the temperature of the reaction kettle is kept constant between 84 and 86 ℃ for 60 min;
(6) then eliminating, neutralizing and discharging.
2. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein in the step (1), the amount of the emulsifier is 1-1.5% of the total amount of the monomers; the dosage of the acrylate monomer is 40-60% of the total amount of the monomer, and the emulsifier comprises one or more of an anionic emulsifier, an anionic non-composite emulsifier and a reactive emulsifier; the crosslinking monomer comprises DAAM or AAEM; the functional monomer comprises acrylic acid or methacrylic acid; the hard monomer comprises one or two of methyl methacrylate and styrene; the soft monomer comprises one or two of butyl acrylate and isooctyl acrylate.
3. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein in the step (2), the amount of the emulsifier is 1-1.5% of the total amount of the monomers; the dosage of the acrylate monomer is 40-60% of the total amount of the monomer, and the emulsifier comprises one or more of an anionic emulsifier, an anionic non-composite emulsifier and a reactive emulsifier; the hard monomer comprises one or two of methyl methacrylate and styrene; the soft monomer comprises one or two of butyl acrylate and isooctyl acrylate; the functional monomer includes acrylic acid or methacrylic acid.
4. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein in the step (3), the initiator is a thermal initiator, the initiator comprises one of ammonium persulfate, sodium persulfate or potassium persulfate, the amount of the initiator is 0.25-0.35% of the total amount of the monomers, and the amount of deionized water is 50-60 times of the amount of the initiator.
5. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein in the step (4), the amount of the pre-emulsion B added is 3-5% of the total amount of the pre-emulsion B prepared in the step (2); the amount of the added initiator solution is 1/5-1/3 of the total amount of the initiator solution prepared in the step (3).
6. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein in the step (5), a dropping pump is adopted to accurately control the dropping speed, and the dropping time is controlled to be 230-240 min.
7. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein the post-eliminating step comprises the steps of cooling the polymerized material of the monomer to 63-65 ℃, adding a certain amount of oxidant and reducer, and keeping the temperature at 65 ℃ for 30 min; wherein the oxidizing agent comprises tert-butyl hydroperoxide, and the reducing agent comprises one of ascorbic acid, sodium formaldehyde sulfoxylate or FF 6M.
8. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 7, wherein the amount of the oxidant is 0.1-0.2% of the total amount of the monomers, and the amount of the reductant is 0.05-0.1% of the total amount of the monomers.
9. The preparation method of the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein the neutralizing step comprises the steps of cooling to below 50 ℃ after the post-eliminating step, adding a certain amount of neutralizing agent, and controlling the pH value to 7.5-8.5 after dripping; the neutralizing agent comprises one of ammonia water, diethanol amine, triethanolamine or AMP-95.
10. The method for preparing the gradient core-shell acrylic emulsion for the outdoor wood lacquer according to claim 1, wherein the discharging step comprises the steps of reducing the temperature to be below 40 ℃ after the neutralizing step, adding a certain amount of bactericide, stirring for 30min, filtering and discharging; the amount of the bactericide is 0.01-0.02% of the total amount of the system, and the bactericide comprises isothiazolinone compounds.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160480A (en) * | 2022-02-14 | 2022-10-11 | 上海金狮化工有限公司 | Waterborne acrylic resin for coloring woodware and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177939A (en) * | 2014-09-05 | 2014-12-03 | 上海展辰涂料有限公司 | Room-temperature self-crosslinking wood lacquer emulsion and preparation method thereof |
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN106832080A (en) * | 2017-02-14 | 2017-06-13 | 中山市博海精细化工有限公司 | A kind of woodcare paint styrene-acrylate core/shell emulsion and preparation method thereof |
| WO2020055371A2 (en) * | 2018-09-11 | 2020-03-19 | Organik Kimya San. Ve Tic. A.Ş. | Polymodal polymer compositions for coating applications |
| CN111072845A (en) * | 2019-12-20 | 2020-04-28 | 珠海展辰新材料股份有限公司 | Emulsion and method for producing the same |
| CN111607035A (en) * | 2020-07-07 | 2020-09-01 | 上海金狮化工有限公司 | Preparation method of acrylate microemulsion and acrylate microemulsion |
-
2021
- 2021-10-28 CN CN202111259035.3A patent/CN113980168B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177939A (en) * | 2014-09-05 | 2014-12-03 | 上海展辰涂料有限公司 | Room-temperature self-crosslinking wood lacquer emulsion and preparation method thereof |
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN106832080A (en) * | 2017-02-14 | 2017-06-13 | 中山市博海精细化工有限公司 | A kind of woodcare paint styrene-acrylate core/shell emulsion and preparation method thereof |
| WO2020055371A2 (en) * | 2018-09-11 | 2020-03-19 | Organik Kimya San. Ve Tic. A.Ş. | Polymodal polymer compositions for coating applications |
| CN111072845A (en) * | 2019-12-20 | 2020-04-28 | 珠海展辰新材料股份有限公司 | Emulsion and method for producing the same |
| CN111607035A (en) * | 2020-07-07 | 2020-09-01 | 上海金狮化工有限公司 | Preparation method of acrylate microemulsion and acrylate microemulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160480A (en) * | 2022-02-14 | 2022-10-11 | 上海金狮化工有限公司 | Waterborne acrylic resin for coloring woodware and preparation method thereof |
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