CN100376607C - Latex type hydroxy acryl acid resin possessing core-shell configuration - Google Patents
Latex type hydroxy acryl acid resin possessing core-shell configuration Download PDFInfo
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Abstract
The present invention relates to an emulsion type hydroxy acryl acid resin with a core-shell structure. The present invention is formed by the emulsion polymerization of four kinds of monomers in the class of olefin under the conditions of existence of initiator and an emulsifying agent; the monomers (1) comprises 60 to 80 wt% of olefin-class monomer without other functional function base groups, 20 to 40 wt% of olefin-class monomer (2) containing hydroxy groups, 2 wt% to 8 wt% of olefin-class monomer (3) containing epoxy groups and 1 wt% to 5 wt% of olefin-class monomer (4) containing carboxyl, wherein 20 to 40 wt% of monomers (1) are used as core monomers; the rest monomers (1) are mixed with the monomers (2), (3) and (4) as monomers forming a shell; then, a core-shell structure is formed. The resin can be used as hydroxyl-group resin with two-component coating and has the advantages of low VOC content, high solid content and improvement in the hardness, the flexibility and various resistance of a formed coating film. The resin is used for coating wood, plastics, metal, glass, concrete, etc.; the resin can replace traditional two-component polyurethane self-drying coating in a solvent type and amino-group baking paint in a solvent type.
Description
Technical Field
The invention relates to an emulsion type hydroxyl-containing acrylic resin with a core-shell configuration, which is particularly suitable for serving as a hydroxyl component in a two-component waterborne wood coating, a waterborne anticorrosive coating and the like.
Background
With the increasing strictness of environmental requirements on a global scale, water-based paint products are applied on a large scale. However, the medium resistance and hardness of the coating film are not effectively improved by the conventional method due to the restriction of the preparation mechanism. Under such circumstances, studies on aqueous hydroxy resins capable of crosslinking by adding a curing agent have been initiated. Compared with the emulsion type hydroxyl-containing acrylic resin synthesized by a solvent method, neutralized salified and water dispersible hydroxyl resin and water soluble polyurethane hydroxyl resin, the emulsion type hydroxyl-containing acrylic resin has low cost and higher solid content, and the key is that the content of Volatile Organic Compounds (VOC) is low. Now, the paint has been widely concerned by research units and paint manufacturers at home and abroad and actively participates in research and development. U.S. Pat. No. 5,5641829 discloses a coating film having good dielectric strength, which is prepared by polymerizing hydroxyethyl acrylate, butyl acrylate and acrylic acid as monomers in a solvent, neutralizing with alkali after the reaction is completed, dispersing in water to form a water-dispersed hydroxyl resin, and crosslinking and curing 243.0 parts and 39.8 parts of a crosslinking agent (trade name Cymel 327) in the presence of a phosphate ester catalyst. However, since the water-dispersible hydroxyl resin is polymerized by a solvent method, the VOC content is high and the solid content is low. International patent application WO 01-72909 relates to an aqueous hydroxyl-containing polymer which is divided into three stages during the polymerization: the first stage monomer composition ratio is methyl methacrylate/butyl acrylate/methacrylic acid 441.6/147.2/11.9, the second stage monomer composition ratio is methyl methacrylate/butyl acrylate/hydroxyethyl acrylate 71.0/35.0/6.9, and the third stage monomer composition ratio is methyl methacrylate/butyl acrylate/hydroxyethyl acrylate/methacrylic acid 12.3/30.8/40.2/22.7; the aluminum powder paint coating obtained by mixing 165 parts of the hydroxyl emulsion, 150 parts of the aluminum powder slurry and 112 parts of the polyurethane dispersoid has good performance, but the synthesis process of the emulsion is complex, and various resistances of the obtained coating cannot be satisfied. The hydroxyl acrylic emulsion with the microgel core structure disclosed in Chinese patent application 200410051550.2 is characterized in that a vinyl silane coupling agent and an acrylate monomer are copolymerized to obtain a core with the microgel structure, then the copolymerization of a hydroxyl-containing vinyl monomer and an acrylate monomer is carried out on the surface of the core, the interior of the core can be self-crosslinked, and the hydroxyl on a shell is used for external crosslinking, so that crosslinking points are increased, the hardness and the resistance of a coating film are improved, but the coating film becomes brittle and the flexibility is poor; all are synthesized by conventional emulsifiers, are easy to foam and influence the water resistance of a coating film; the microgel structure can enhance the activity of the system, and the service life of the prepared coating is short and is only 3-6 hours.
Disclosure of Invention
The invention aims to provide an emulsion type hydroxyl-containing acrylic resin with a core-shell structure, which has low VOC content and high solid content, and the hardness, flexibility and various resistances of a formed coating film are improved.
The technical scheme for realizing the purpose of the invention is as follows: an emulsion type hydroxyl-containing acrylic resin with a core-shell configuration is prepared by emulsion polymerization of the following 4 vinyl monomers in the presence of an initiator and an emulsifier, wherein the monomer types and the monomer use amounts account for the following percentages in the total monomer amount: (1) 60 to 76.06 percent of alkene monomer without other functional groups; (2) 20 to 40 percent of alkene monomer containing hydroxyl; (3) 2 to 8 percent of alkene monomer containing epoxy group; (4) 1 to 5 percent of vinyl monomer containing carboxyl;
the amount of the initiator is 0.2 to 0.7 percent of the total amount of the monomers;
the emulsifier is a reactive emulsifier, or the reactive emulsifier and a conventional micromolecular emulsifier, and the weight ratio of the two is 7.5-15.0: 1; the total dosage of the emulsified wattle accounts for 0.3 to 2.0 percent of the total amount of the monomers;
during emulsion polymerization, 20-40% of monomer (1) is firstly polymerized into seed emulsion serving as a core, the rest monomer (1) is mixed with monomers (2), (3) and (4) to serve as a shell-forming monomer, and a shell is polymerized on the surface of formed core particles to form a core-shell configuration;
the above percentages are weight percentages.
The monomer (1) is: two or more of acrylate or methacrylate monomers and aromatic vinyl monomers. (meth) acrylic acid ester-based monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and lauryl (meth) acrylate; aromatic vinyl monomers such as styrene, methylstyrene and vinyltoluene.
The emulsion type hydroxyl-containing acrylic resin is prepared by the following monomers in percentage by weight: 22 to 26 percent of vinyl monomer containing hydroxyl group (2); 3 to 5 percent of alkene monomer containing epoxy group; a carboxyl group-containing vinyl monomer (4) in an amount of 1 to 2%.
The emulsion type hydroxyl-containing acrylic resin is characterized in that the hydroxyl-containing vinyl monomer (2) is: one or more of hydroxyl ester monomers of acrylic acid or methacrylic acid. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like.
The emulsion type hydroxyl-containing acrylic resin is characterized in that the epoxy group-containing vinyl monomer (3) is: one or more of glycidyl ester monomers of acrylic acid or methacrylic acid. For example, glycidyl (meth) acrylate, allyl glycidyl ester, and the like.
The emulsion type hydroxyl-containing acrylic resin is characterized in that the vinyl monomer (4) containing carboxyl is: one or more of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
The emulsion type hydroxyl-containing acrylic resin is characterized in that the reactive emulsifier is one or more of anionic or nonionic reactive emulsifying monomers, such as: sodium methacrylamidoisoproylsulfonate, SE-10N, NE-10 and the like, and conventional small-molecule emulsifiers such as: sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and the like.
The emulsion type hydroxyl-containing acrylic resin is characterized in that the initiator is persulfate, such as:
ammonium persulfate, potassium persulfate, and the like.
The emulsion type hydroxyl-containing acrylic resin is milky white micro-transparent blue-light liquid, has the appearance of 200-2000 Mpa & s, the solid content of 42-46%, the pH value of 7.0-8.5, the particle size of 0.05-0.2 mu m, the VOC content of volatile organic compounds of less than 0.1%, the hydroxyl content of 2.5-3.5% and the storage period of more than 6 months.
The emulsion type hydroxyl-containing acrylic resin can be produced by the existing emulsion polymerization equipment.
When the resin is prepared, firstly, the resin is heated in the presence of an emulsifier and an initiator, 20-40% of the monomer (1) is polymerized to form a core emulsion, then, the emulsifier, the initiator and the mixture of the residual monomer (1), the monomer (2), the monomer (3) and the monomer (4) are simultaneously dripped at the same temperature, the monomers are polymerized on the surfaces of particles to form a shell containing hydroxyl, epoxy and carboxyl, the carboxyl is salified after neutralization, functional groups (hydroxyl and epoxy) are reserved in the shell, and finally, the emulsion type hydroxyl-containing acrylic resin with the core-shell configuration is formed.
The invention has the technical effects that: the emulsion type hydroxyl-containing acrylic resin with the core-shell configuration has the following beneficial effects: one is that because the resin of the invention is emulsion type, in the formulation design, water is used as dispersing medium, no organic solvent is added, therefore compared with the water dispersion type hydroxy acrylic resin (VOC content is more than 10%) formed by polymerization by solvent method used in China at present, the invention is safe, nontoxic and environment-friendly (VOC content is less than 0.1%), in addition, because the water dispersion type hydroxy acrylic resin formed by polymerization by solvent method has the problem of dilution peak, the solid content is less than 40%, but the solid content of the resin of the invention can reach 46% at most, which can indirectly improve the construction efficiency. And the reactive emulsifying monomer or the reactive emulsifying monomer and a very small amount of conventional small molecular emulsifying agent are used as the emulsifying agent of the system, so that the advantages of the emulsion are that the foaming property is low, and the water resistance and the transparency of a coating film are improved. Thirdly, the resin has a standard core-shell configuration, and since the vinyl monomer containing proper functional groups is determined to be used as a nucleating monomer during the formulation design; determining the using amount of each monomer; determining the proper quantity of the vinyl monomer without other functional groups as a nuclear monomer; in practice, after polymerization of the core, the remaining vinyl monomer containing no functional group is added together with the hydroxyl group-containing vinyl monomer, the carboxyl group-containing vinyl monomer, and the epoxy group-containing vinyl monomer, so that an appropriate amount of functional groups (hydroxyl group and epoxy group) can be distributed on the surface layer of the latex particles after emulsion polymerization of the shell. When the resin is used as a hydroxyl component of a two-component coating, the hydroxyl of the shell layer can fully participate in the reaction, the crosslinking efficiency of the formed coating film is improved, the hardness and various resistances of the coating film are improved, and the polymer serving as the core does not participate in the crosslinking reaction during film forming, so that the coating film has good flexibility; at the same time, the activity of the polymer as the core is low, so that the prepared coating has longer service life (more than 24 hours). And fourthly, epoxy groups introduced into the shell layer further increase the hardness of the coating film and various medium resistances of the coating film.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but is not limited thereto.
The parts in the formulations of the examples and the comparative examples are parts by weight; all raw materials are coating grade commercial products unless otherwise specified; the deionized water meets the requirements specified in the GB6682-92 three-stage water (pH is 5.0-7.5, and the conductivity is less than or equal to 0.50 mS/m).
Examples 1 to 3:
the formula is shown in Table 1
TABLE 1
| Material(s) Number of | Name of raw materials | Example 1 (parts) | Example 2 (share) | Example 3 (share) | |
| 1 (medium) Quality) | Deionized water | 160.0 | 160.0 | 140.0 | |
| 2 (milk) Agent for treatment of chemical And a lead Hair agent) | Deionized water | 20.0 | 20.0 | 20.0 | |
| SE-10N | / | 0.6 | 0.3 | ||
| NE-10 | / | / | 0.3 | ||
| AMPS (active ingredient 50%) | 1.2 | / | / | ||
| Sodium dodecyl sulfate | 0.2 | / | / | ||
| Ammonium persulfate | 0.3 | 0.3 | 0.3 | ||
| 3 (Cheng) Nuclear bill Body (1) | Methacrylic acid methyl ester | 20.0 | 10.0 | 2.0 | |
| Acrylic acid butyl ester | 15.0 | 20.0 | 15.0 | ||
| Styrene (meth) acrylic acid ester | / | / | 12.0 | ||
| 4 (milk) Agent for chemical treatment And a lead Hair agent) | Deionized water | 30.0 | 30.0 | 30.0 | |
| SE-10N | / | 1.2 | 1.0 | ||
| NE-10 | / | / | 1.0 | ||
| AMPS (active ingredient 50%) | 2.8 | / | / | ||
| Ammonium persulfate | 0.5 | 0.5 | 0.5 | ||
| 5 ( Become into Shell Sheet Body ) | Sheet Body ① | Methacrylic acid methyl ester | 45.0 | 30.0 | 5.0 |
| Acrylic acid butyl ester | 35.0 | 50.0 | 40.0 | ||
| Styrene (meth) acrylic acid ester | / | / | 35.0 | ||
| Sheet Body ② | Hydroxypropyl acrylate | 30.0 | / | / | |
| Hydroxyethyl methacrylate | / | 35.0 | 40.0 | ||
| Sheet Body ③ | Glycidyl methacrylate Esters | 3.0 | 6.0 | 4.0 | |
| Sheet Body ④ | Acrylic acid | 3.2 | / | / | |
| Methacrylic acid | / | 2.2 | 1.6 | ||
| 6 (middle) Mixture) | Aqueous ammonia | 2.6 | 1.6 | 1.0 |
Note:
example 1: the monomer (1) accounts for 76.06 percent; monomer (2) accounts for 19.84%; the monomer (3) accounts for 1.98 percent; the monomer (4) accounts for 2.12 percent; the emulsifier accounts for 1.46 percent of the total amount of the monomers; the initiator accounts for 0.53 percent of the total amount of the monomers;
example 2: 71.80 percent of the monomer (1); the monomer (2) accounts for 22.84 percent; 3.92 percent of monomer (3); 1.44% of monomer (4); the emulsifier accounts for 1.17 percent of the total amount of the monomers; the initiator accounts for 0.52 percent of the total amount of the monomers;
example 3: the monomer (1) accounts for 70.51 percent; the monomer (2) accounts for 25.87%; the monomer (3) accounts for 2.59 percent; the monomer (4) accounts for 1.03 percent; the emulsifier accounts for 1.68 percent of the total amount of the monomers; the initiator accounts for 0.52 percent of the total amount of the monomers;
AMPS is an anionic reactive emulsifying monomer from luobo, usa:
the molecular formula is as follows: CH (CH) 2 ＝CH-CO-NH-C(CH 3 ) 2 -CH 2 -SO 3 Na (sodium methacrylamide isopropyl sulfonate) 50 percent of effective components;
in the table SE-10N is an anionic reactive emulsifying monomer from Asahi Denka Japan:
the molecular formula is as follows:
100% of active ingredient;
NE-10 in the table is a nonionic reactive emulsifying monomer from Asahi Denka Kogyo
The molecular formula is as follows:
100% of active ingredients.
The synthesis process comprises the following steps:
adding the material 1 according to the formula amount in the table 1 into a 500ml three-mouth bottle provided with a heating device, a stirring device, a thermometer and a condensing device, heating to 80 ℃, adding the material 2, dripping the material 3 within 1 hour, and keeping the temperature for 0.5 hour after dripping to generate the seednuclear emulsion. Then, the materials 4 and 5 were added dropwise at the same time at the above temperature, and the addition was completed within 3 hours. After dripping, the temperature is kept for 2 hours. Then cooling to 50 ℃, adding the material 6 for neutralization, filtering and discharging after uniform stirring to respectively prepare the resin of the invention of the embodiments 1-3, and the technical indexes are shown in table 2.
Comparative example
The comparative example is a hydroxyl-containing acrylic resin prepared by a conventional emulsion polymerization process with a conventional small molecular emulsifier, and no vinyl monomer with an epoxy group is added in the formula.
The formula is as follows: (1) 160.0 parts of deionized water, (2) 50.0 parts of deionized water, 1.6 parts of sodium dodecyl sulfate and 0.6 part of ammonium persulfate, (3) 65.0 parts of methyl methacrylate, 55.0 parts of butyl acrylate, 30 parts of hydroxypropyl acrylate and 2.7 parts of acrylic acid, and (4) 2.0 parts of ammonia water;
adding the material (1) into a 500ml three-mouth bottle provided with a temperature rising device, a stirring device, a thermometer and a condensing device, rising the temperature to 80 ℃, simultaneously dripping the material (2) and the material (3), and finishing dripping within 3 hours. After dripping, the temperature is kept for 2 hours. Then cooling to 50 ℃, adding the material (4) for neutralization, uniformly stirring, filtering and discharging to obtain the hydroxyl-containing acrylic resin of the comparative example, wherein the technical indexes are shown in Table 2.
TABLE 2
| Index (es) | Example 1 | Example 2 | Example 3 | Comparative example |
| Appearance of the product | Milk white, light and transparent blue Light (A) | Opalescent blue light intensity | Opalescent blue light intensity | Opalescent blue light intensity |
| A coagulation rate% | ＜0.2 | ＜0.1 | ＜0.2 | ＜0.2 |
| Viscosity, mpa.s | 300 | 360 | 1200 | 680 |
| Solid content of% | 42.1 | 42.5 | 44.2 | 42.2 |
| Hydroxyl content% | 2.6 | 3.0 | 3.4 | 2.6 |
| pH value | 8.3 | 7.8 | 8.0 | 8.2 |
| Average particle diameter, μm | 0.15 | 0.08 | 0.10 | 0.10 |
| VOC content% | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Storage period of month | ＞6 | ＞6 | ＞6 | ＞6 |
Examination of film Performance after film formation
A two-component polyurethane coating (the coating of examples 1 to 3 had a service life of at least 24 hours) was prepared by using 100g of the above resin as a hydroxyl component and 10g of a polyisocyanate component B2336 (BAYER Corp., NCO content: 18%), coating the resulting coating on a tin plate to a thickness of 20 μm (dry film), and after drying at 25 ℃ and a humidity of 50% for 10 days, the coating properties were examined, and the results are shown in Table 3.
TABLE 3
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example | Detection method |
| Appearance of the product | Transparent and flat Machine for finishing | Transparent and flat Machine for finishing | Transparent and flat Finishing machine | Transparent and flat Machine for finishing | Visual inspection of |
| Adhesion force, grade | 0～1 | 0～1 | 0～1 | 0～1 | GB/T9286-1998 |
| Flexibility, mm | 1 | 1 | 1 | 2 | GB/T1731-93 |
| Hardness of pencil | 2H | H | 2H | H | GB/T6739-1996 |
| Water resistance, 72h | Without change | Without change | Without change | Whitening of rice | Note 1 |
| The extraction rate of the acetone is high, ％ | ＜10 | ＜10 | ＜10 | ＞30 | note 2 |
Note 1: water resistance detection method
Coating different emulsion polymers on 8cm × 12cm glass plates respectively to obtain a coating film with a thickness of about 20 μm, drying at 25 deg.C for 7 days, soaking in deionized water, and observing the whitening, foaming and peeling conditions of the coating film.
Note 2: acetone extraction rate detection method
The emulsion is added in the weight of m 0 After curing the film formed on the glass plate, the plate was weighed (m) 1 ) Then immerging in a large amount of acetone solution, standing for 7 days, taking out, drying, and weighing (m) 2 ) The acetone extraction rate (f) was calculated by the following formula.
Because the reactive emulsifying monomer is used, the water resistance of the coating is improved, the core-shell structure of the latex particles, the shell hydroxyl and epoxy functional groups fully participate in the crosslinking reaction, the crosslinking degree and the hardness of the coating are improved, and the inner core layer polymer does not participate in the crosslinking reaction to endow the coating with good flexibility, so that the crosslinking degree, the flexibility and the water resistance of the coating formed by the resin are obviously improved compared with those of a comparative example. The emulsion type hydroxyl-containing acrylic resin can be used as a hydroxyl component to prepare various two-pack bi-component coatings, can be baked and cured at 120-180 ℃ and can also be cured at normal temperature, and can be widely used for various base materials, such as: coating the surfaces of wood, plastic, metal, glass, concrete and the like. Can replace the traditional solvent-based two-component polyurethane self-drying paint and solvent-based amino baking paint.
Claims (6)
1. An emulsion type hydroxyl-containing acrylic resin with a core-shell configuration is characterized in that: the emulsion is prepared by emulsion polymerization of the following 4 vinyl monomers in the presence of an initiator and an emulsifier, wherein the types of the monomers and the use amount of each monomer account for the following percentage in the total amount of the monomers: (1) 60 to 76.06 percent of alkene monomer without other functional groups; (2) 20 to 40 percent of alkene monomer containing hydroxyl; (3) 2 to 8 percent of alkene monomer containing epoxy group; (4) vinyl monomer containing carboxyl 1-5%;
the amount of the initiator is 0.2 to 0.7 percent of the total amount of the monomers;
the emulsifier is a reactive emulsifier, or the reactive emulsifier and a conventional micromolecular emulsifier, and the weight ratio of the two is 7.5-15.0: 1; the total dosage of the emulsifier is 0.3-2.0% of the total amount of the monomers;
during emulsion polymerization, 20-40% of monomer (1) is firstly polymerized into seed emulsion serving as a core, the rest monomer (1) is mixed with monomers (2), (3) and (4) to serve as a shell-forming monomer, and a shell is polymerized on the surface of formed core particles to form a core-shell configuration;
the monomer (1) is two or more of acrylate or methacrylate monomers and aromatic vinyl monomers;
the monomer (2) is one or more than one of hydroxyl ester monomers of acrylic acid or methacrylic acid;
the above percentages are weight percentages.
2. An emulsion-type hydroxyl-containing acrylic resin according to claim 1, characterized in that: the following monomers are used in percentage by weight in the total amount of the monomers: 22 to 26 percent of vinyl monomer containing hydroxyl group (2); 3 to 5 percent of alkene monomer containing epoxy group; a carboxyl group-containing vinyl monomer (4) in an amount of 1 to 2%.
3. An emulsion-type hydroxyl-containing acrylic resin according to claim 1 or 2, characterized in that: the alkene monomer (3) containing the epoxy group is one or more of glycidyl ester monomers of acrylic acid or methacrylic acid.
4. The emulsion type hydroxyl-containing acrylic resin according to claim 1 or 2, characterized in that: the vinyl monomer (4) containing carboxyl is one or more of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
5. The emulsion type hydroxyl-containing acrylic resin according to claim 1 or 2, characterized in that: the reactive emulsifier is one or more than one of anionic or nonionic reactive emulsifying monomers.
6. An emulsion-type hydroxyl-containing acrylic resin according to claim 1 or 2, characterized in that: the appearance of the blue-light-transmitting liquid is milk white slightly transparent blue-light liquid, the viscosity is 200-2000 Mpa.s, the solid content is 42-46%, the pH value is 7.0-8.5, the particle size is 0.05-0.2 mu m, the VOC content of volatile organic compounds is less than 0.1%, the hydroxyl content is 2.5-3.5%, and the storage period is more than 6 months.
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| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN1624009A (en) * | 2004-09-21 | 2005-06-08 | 华南理工大学 | Hydroxyl acrylic acid emulsion with microgel nuclear structure and preparation process and application thereof |
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| CN1800225A (en) | 2006-07-12 |
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