CN115717014B - Preparation method of easily-crosslinked core-shell polyhydroxyacrylate emulsion coating - Google Patents
Preparation method of easily-crosslinked core-shell polyhydroxyacrylate emulsion coating Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 61
- 239000011258 core-shell material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 23
- 239000012792 core layer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
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- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000000178 monomer Substances 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000007731 hot pressing Methods 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 25
- 239000003973 paint Substances 0.000 abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 14
- 125000003700 epoxy group Chemical group 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 11
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
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- 229920000058 polyacrylate Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000001680 brushing effect Effects 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
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- 125000000524 functional group Chemical group 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method of an easily cross-linked core-shell polyhydroxyacrylate emulsion coating. According to the method, three groups of epoxy groups, carboxyl groups and hydroxyl groups are introduced through glycidyl methacrylate, acrylic acid and hydroxypropyl methacrylate, the active interaction between the epoxy groups and the hydroxyl groups at the polymerization temperature is avoided by virtue of the advantages of a core-shell structure and the characteristics of the groups, the hydrophobic epoxy groups, the hydrophilic carboxyl groups and the hydrophilic hydroxyl groups are reserved in the core layer and the shell layer to the greatest extent through the core-shell structure, the maximum separation of crosslinking groups in the polymer is realized, and therefore the storage stability of the coating is enhanced. The invention realizes synchronous improvement of the performances of the paint in the aspects of adhesive force, hardness, storage stability and the like.
Description
Technical field:
the invention relates to the field of decorative paint. In particular to a preparation method of a core-shell type polyhydroxyacrylate coating which is rapidly crosslinked by hot pressing.
The background technology is as follows:
the wood lacquer is a paint applied to the surface of wood furniture and has important significance for protecting and decorating the furniture surface. The paint has oily water, and the water paint has been developed rapidly by virtue of low VOC emission. Emulsion polymers are the main film forming materials of the water-based wood lacquer, and common film forming resins include polyurethane resin, alkyd resin, epoxy resin, acrylic resin and the like. The acrylic ester monomers are various, double bonds are generally utilized for free radical polymerization in the synthesis process to prepare acrylic ester emulsion with small particle size distribution and strong stability, active groups such as carboxyl, hydroxyl, epoxy groups and the like are introduced into the emulsion by virtue of functional monomers such as acrylic acid, hydroxypropyl methacrylate, glycidyl methacrylate and the like, more crosslinking sites are provided for the subsequent hot-pressing veneering process of wood furniture, and the comprehensive performance of the coating can be improved by reacting in a self-crosslinking or external crosslinking mode. The water-based acrylic ester wood coating can realize the regulation and control of emulsion performance by changing the types and the dosage of the monomers. The solvent resistance and the mechanical strength of the monomer can be better than those of the aqueous polyurethane resin coating by adjusting the types of the monomers, and the film-forming hardness of the monomer is better than that of the alkyd resin coating by increasing the occupation ratio of the hard monomer raw materials, so that the monomer has low price and stronger market competitiveness compared with the aqueous epoxy resin coating. In addition, the acrylate coating also has the advantages of high glossiness, good stability, strong weather resistance and the like, and the acrylate coating synthesized by the emulsion polymerization method takes water as a solvent, so that the dosage of organic matters is greatly reduced, the environment is protected, the addition and release of formaldehyde-free compounds are basically realized, the storage stability of emulsion is improved, the storage time of the product is longer, and the waste of resources is reduced to a certain extent (China forestry science institute, 2019-04-01). However, the existing polyacrylate coating still has the problems of low crosslinking degree, overlong crosslinking time, poor wear resistance of the coating and the like. Therefore, in order to overcome the limitations of these disadvantages in application, it is generally necessary to modify the polyacrylate by introducing functional monomers or the like. The polyacrylate emulsion containing the hydroxyl functional monomer can form an external crosslinking system with amino resin, epoxy resin and the like, so that the crosslinking density of the film-forming material is improved, and the performance of the coating is improved; the polyacrylate emulsion containing the hydroxyl functional monomer can also be further modified to form an intramolecular self-crosslinking system (Journal of Applied Polymer Science,2017,134 (21), 44844). The existing common self-crosslinking methods are three, namely, the method is based on the method that N-methyl acrylamide (NMA) monomers are introduced into a polymer to form a self-crosslinking system, but formaldehyde is easy to release in the crosslinking process, so that the method poses a threat to human bodies. The use of N-ethylacrylamide instead of NMA can completely eliminate formaldehyde, but acetaldehyde is also formed, so that the molecular weight of the formed polymer is too low to meet the requirements of industry on the mechanical strength of the coating. Secondly, a cross-linking system based on acetoacetic acid groups, namely acetoacetoxy ethyl methacrylate (AAEM) is a common functional group, but the system formed by the method can be self-cross-linked at room temperature, the storage stability of the coating is poor, and the addition of a polymerization inhibitor can prolong the shelf life, but can cause serious delayed solidification phenomenon in the use process. Thirdly, a self-crosslinking system based on ketone-hydrazide reversible reaction, the reaction speed of the method is relatively slow, the mechanical property improving effect is poor, and toxic hydrazine also causes harm to human bodies (ACS applied materials and interfaces,2016,8 (27), 17499-17510), so that the method is difficult to adapt to the industrial production requirements.
The wood coating is an indispensable part of the furniture industry, not only can play a role in decorating and beautifying the protection plate, but also can improve the physical and mechanical properties of the plate, and achieves the purposes of aging resistance and service life prolongation (Journal of Applied Polymer Science 2020,137 (31), 48931). There is an increasing demand for green environmental protection paint in the current market, and a formaldehyde-free environmental protection paint with excellent mechanical properties, high gloss and good adhesion needs to be developed.
The invention comprises the following steps:
aiming at the problems of poor storage stability, poor crosslinking performance and the like of the existing wood furniture coating, the invention develops a hot-pressing quick crosslinking wood furniture resin coating. The innovation point of the method is that three groups of epoxy groups, carboxyl groups and hydroxyl groups are introduced through glycidyl methacrylate, acrylic acid and hydroxypropyl methacrylate, and the active interaction of the epoxy groups and the hydroxyl groups at the polymerization temperature is avoided by virtue of the advantages of a core-shell structure and the characteristics of the groups, and the hydrophobic epoxy groups, the hydrophilic carboxyl groups and the hydroxyl groups are furthest reserved in a core layer and a shell layer respectively through the core-shell structure, so that the maximum separation of crosslinking groups in the polymer is realized, and the storage stability of the coating is enhanced. Epoxy groups only react with carboxyl groups at the polymerization reaction temperature, and the residual epoxy groups can react with hydroxyl groups under the hot-pressing condition, so that secondary crosslinking of the polyhydroxyacrylate emulsion is realized, a double crosslinking system is formed, and the synchronous improvement of performances in the aspects of paint adhesion, hardness, storage stability and the like is realized.
The technical scheme of the invention is as follows:
a preparation method of an easily cross-linked core-shell polyhydroxyacrylate emulsion coating comprises the following steps:
(1) Mixing the core layer monomer and the first emulsion, and stirring to obtain core layer pre-emulsion;
mixing the shell monomer with the second emulsion, and stirring to obtain a shell pre-emulsion;
the stirring speed is 1500-2000 r/min; stirring for 20-30 minutes;
in the nuclear layer pre-emulsion, the mass ratio is that the first emulsion: nuclear layer monomer= (2-3): (5-6);
in the shell layer pre-emulsion, the mass ratio is as follows: shell monomer= (2-3): (5-6);
the core layer monomer is a mixture of two or three of methyl methacrylate, butyl acrylate and glycidyl methacrylate, and the mass ratio of the methyl methacrylate is as follows: butyl acrylate: glycidyl methacrylate= (50-20): (0-20): (1-10); when the amount of the substance is 0, the substance is not added;
the shell monomer is a mixture of methyl methacrylate, butyl acrylate, acrylic acid and hydroxypropyl methacrylate, and the mass ratio of the methyl methacrylate is as follows: butyl acrylate: acrylic acid: hydroxypropyl methacrylate= (30-20): (30-20): (1-3): (1-8);
(2) Adding sodium bicarbonate and a third emulsion into a reactor, respectively dripping 25-35% by volume of nuclear layer pre-emulsion and 25-35% by volume of ammonium persulfate solution into the reactor for 15-20 min under the condition of nitrogen atmosphere and electromagnetic stirring at 75-80 ℃, keeping the reaction temperature at 75-80 ℃ and preserving the temperature for 0.5-1 h to form seed emulsion;
adding 0.5-1 g sodium bicarbonate into every 30g third emulsion;
the first emulsion, the second emulsion and the third emulsion are the same in emulsifier, and are sodium dodecyl sulfate and OP-10 in mass ratio: OP-10=2: 1, a step of; the mass concentration of the first emulsion, the second emulsion and the third emulsion is the same or different and is 3 to 6 percent;
the mass ratio of the core layer pre-emulsion to the shell layer pre-emulsion is 1:0.9-1.1;
the mass ratio of the core layer pre-emulsion to the ammonium persulfate solution is (7-9): (1-1.5); the mass concentration of the ammonium persulfate solution is 0.10-0.18%;
the mass ratio of the first emulsion to the second emulsion to the third emulsion is 1:0.9-1.1:0.9-1.1;
(3) Then heating to 80-85 ℃, dropwise adding the nuclear layer pre-emulsion and 25-35% ammonium persulfate solution into the seed emulsion, and preserving heat for 0.5-1 h when the time is 1.5-1.75 h, thus finishing the nuclear layer preparation; then dropwise adding the shell pre-emulsion and the residual ammonium persulfate solution at the temperature of 80-85 ℃ for 2-2.25 h, carrying out heat preservation reaction for 0.5-1 h, then cooling to room temperature, and regulating the pH value of the emulsion to 8-9 to obtain stable core-shell polyhydroxyacrylate emulsion which is milky;
the core-shell polyhydroxyacrylate emulsion prepared by the method is applied to the surface coating of wood furniture.
The method specifically comprises the following steps: the prepared core-shell type polyhydroxyacrylate emulsion is directly brushed on the front surface of the decorative paper, then the decorative paper is quickly dried in an oven at 120 ℃ for about 30 to 60 seconds, the decorative paper is taken out and placed at room temperature, the core-shell type polyhydroxyacrylate emulsion is brushed on the surface of the artificial board, the back surface of the decorative paper is attached to the artificial board, and the decorative paper is hot-pressed for 3 to 8 minutes under the conditions of 1.5 to 2.0MPa and 120 to 160 ℃.
The invention has the substantial characteristics that:
aiming at the technical problem of decorative paper surface coating, the invention modifies the traditional polyacrylate emulsion, and according to the polymerization reaction of acrylic ester monomers, three functional groups of hydroxyl, carboxyl and epoxy are introduced into a system by means of hydroxypropyl methacrylate, acrylic acid and glycidyl methacrylate functional monomers, and the coating with stable performance is obtained by preparing the polyhydroxyacrylate emulsion with a core-shell structure. The surface coating of decorative paper with excellent comprehensive performance can be obtained by brushing the surface coating on the surface of decorative paper through a hot pressing technology, and compared with a monodisperse polyacrylate coating, the adhesive force of the surface coating is obviously improved.
The beneficial effects of the invention are as follows:
the invention has the beneficial effects that the obtained core-shell polyhydroxyacrylate emulsion has good storage stability and quick crosslinking capability. In the preparation process, the epoxy groups in the glycidyl methacrylate have an important influence on the crosslinking effect in the hot pressing process. The prepared emulsion was characterized for different properties, with the following results. Firstly, for the solid content, the solid content of the polyhydroxyacrylate emulsion with a core-shell structure is 48% (w) which is obviously higher than 40% (w) of the monodisperse polyacrylate emulsion, so that the drying time of a coating film is shortened; secondly, in terms of adhesion performance, the adhesion after coating of the core-shell type polyhydroxyacrylate emulsion is obviously improved compared with that of a monodisperse polyacrylate coating, and according to GB/T9286-1998, the adhesion of the coating film reaches the 0-level standard; in addition, the water resistance and alcohol resistance of the emulsion coating film prepared herein meet the requirements of 48 hours on no foaming and no whitening, and the storage stability is as long as half a year, thereby meeting the requirements of the current national standard on the surface coating film of the decorative paper. Therefore, the core-shell type polyhydroxyacrylate emulsion is used as a coating, so that the surface of the decorative paper can be well protected, and the core-shell type polyhydroxyacrylate emulsion has important significance for decoration of wood furniture.
Drawings
FIG. 1 is a graph of adhesion test after coating of commercial polyhydroxyacrylate emulsions;
FIG. 2 is a graph showing the adhesion test after coating the core-shell polyhydroxyacrylate emulsion obtained in example 3;
FIG. 3 is a graph showing the IR spectrum of the core-shell polyhydroxyacrylate emulsion obtained in example 3 before and after hot pressing.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description is intended to illustrate the invention, and not to limit the invention.
The paint has the main effects of improving the surface glossiness, adhesive force and wear resistance of the wood furniture, improving the aesthetic property of the furniture, prolonging the service life of the furniture, adopting a brush coating and hot pressing combined mode for veneering decoration, requiring a plurality of crosslinking reaction groups in the polyhydroxyacrylic ester emulsion, and improving the performance of the paint by utilizing thermal crosslinking.
The core-shell polyhydroxyacrylate emulsion can form a layer of protective film with stronger adhesive force on the surface of decorative paper in a short time through brushing and hot pressing operation. Functional groups which are easy to react are separated through a core-shell structure, so that the storage time of emulsion is prolonged, the addition of glycidyl methacrylate provides a basis for forming a more compact three-dimensional network structure coating film in the hot pressing process, and meanwhile, the glossiness of the surface of decorative paper after the coating film is improved due to the characteristics of substances.
The reaction process of the invention is shown in the formula: and (3) forming seed emulsion in advance of the nuclear layer pre-emulsion formed by methyl methacrylate, butyl acrylate and glycidyl methacrylate at the temperature of 75 ℃, then heating to 80 ℃, and completing the nuclear layer preparation within 2 hours, wherein the nuclear layer reaction is shown as (1). And (3) maintaining the temperature at 80 ℃, adding a shell pre-emulsion formed by methyl methacrylate, butyl acrylate, methacrylic acid and hydroxypropyl methacrylate into a reaction device within 2.5h to complete shell preparation, cooling to room temperature after the shell reaction is completed as shown in (2), and regulating the pH value by ammonia water to obtain the stable core-shell polyhydroxyacrylate emulsion.
The following examples are methods for preparing high temperature fast cross-linked polyhydroxyacrylate emulsions.
Example 1
The preparation and application of the easily cross-linked core-shell polyhydroxyacrylate emulsion are characterized by comprising the following steps:
90g of deionized water and 3g of emulsifier (OP-10: sds=1:2) were added to a 500ml flask and stirred for 5min at a rate of 500r/min to form an emulsion.
Preparation of core layer pre-emulsion: 50g of methyl methacrylate and 1g of glycidyl methacrylate as core layer monomers were added to a beaker containing 31g of the emulsion obtained above and stirred at a stirring speed of 2000r/min for 15min of pre-emulsification to form a core layer pre-emulsion.
Preparation of shell layer pre-emulsion: 31g of the emulsion obtained above, 24g of methyl methacrylate, 26g of butyl acrylate, 1g of acrylic acid and 1.5g of hydroxypropyl methacrylate are stirred in a beaker, and the stirring speed is 2000r/min, and pre-emulsified for 15min, so as to form a shell pre-emulsion;
(1) 31g of the emulsion (i.e., the remaining 1/3 emulsion) and 0.5g of sodium hydrogencarbonate were added to a four-necked flask and stirred for 5 minutes. When the temperature was raised to 75 ℃, 1/3 of ammonium persulfate solution (a solution composed of 0.25g of ammonium persulfate and 15g of deionized water) and 1/3 of the core layer pre-emulsion were simultaneously added dropwise with a constant pressure dropping funnel for 15 minutes. After the dripping is finished, the temperature is adjusted to 80 ℃, and the temperature is kept for 30 minutes to form seed emulsion.
(2) The residual nuclear layer pre-emulsion is dripped into the seed emulsion for 1.5 hours, and 1/3 ammonium persulfate solution is synchronously dripped for 1.75 hours. After the dripping is finished, stirring and preserving heat for 0.5h at the temperature of 85 ℃ to complete the polymerization of the nuclear layer stage.
(3) The shell pre-emulsion was added dropwise to the reaction vessel over 2 hours with simultaneous dropwise addition of the remaining ammonium persulfate solution over 1.75. 1.75h. After the completion of the dropwise addition, the temperature was adjusted to 90℃and the mixture was stirred and kept at the temperature for 0.5h. And cooling the product to room temperature, regulating the pH value to 8-9, filtering and discharging to obtain the core-shell polyhydroxyacrylate emulsion.
Example 2
Other steps are the same as in example 1, except that the monomer type and the dosage of the core layer are regulated and controlled, and the dosage of the glycidyl methacrylate of the core layer is changed from 1g to 5g; the dosage of methyl methacrylate is changed from 50g to 35g; butyl acrylate was changed from 0g to 10g;
example 3
Other steps are the same as in example 1, except that the monomer type and the dosage of the core layer are regulated and controlled, the dosage of the glycidyl methacrylate of the core layer is changed from 1g to 10g, and the dosage of the methyl methacrylate is changed from 50g to 20g; butyl acrylate was changed from 0g to 20g;
comparative example 1
The adhesive force performance test of the commercial polyacrylate paint comprises the following steps of
Firstly, an artificial board with the specification of 10cm x 10cm is taken as a base material, a commercial polyacrylate coating (model 22687 of Ji-nan Xin-sen chemical industry Co., ltd.) is brushed on the surface of decorative paper, then commercial polyhydroxyacrylate emulsion is brushed on the surface of the artificial board for veneering hot pressing, a QFH-HG600 type adhesive force tester is used for testing, and the testing conditions are that: the blade is 2mm and 11 teeth. The tip of the blade is vertically contacted with the surface of the coating and forms 45 degrees with the grain of the decorative paper, the cutter is pulled at a constant speed for at least 30mm distance, a downward force is always kept, the plate is rotated for 90 degrees, the operation is repeated in the above cutting area, the small square lattice with a fixed area is cut on the surface of the coating and penetrates to the base material, the surface of the coating is lightly scanned several times along the diagonal line of the lattice by using a soft brush, the evaluation is carried out by taking the cross-cut experiment of the paint and varnish film of GB/T9286-1998 as a standard, the parallel experiment is carried out three times, as shown in the attached figure 1, the cutting edge part of the coating is observed to fall off in large fragments, and the affected cross-cut area accounts for 20 percent of the total cross-cut area and is between 15 percent and 35 percent, therefore, the adhesive force rating is evaluated to be 3 grade.
Comparative example 2
An adhesive force performance test of an easily cross-linked core-shell polyhydroxyacrylate emulsion comprises the following steps of
Taking an artificial board with the specification of 10cm x 10cm as a base material, brushing a small amount of core-shell polyhydroxyacrylate emulsion obtained in example 3 on the surface of decorative paper, drying, brushing the core-shell polyhydroxyacrylate emulsion on the surface of the artificial board, performing veneering hot pressing, and testing by using a QFH-HG600 type adhesive force tester after finishing, wherein the testing conditions are as follows: the blade is 2mm and 11 teeth. As shown in FIG. 2, it was observed that the cut edge of the coating was smooth, and was free from falling off, and its adhesion rating was rated as 0 according to GB/T9286-1998, cross-hatch test of paint film for color paint and varnish, which was in accordance with national standard and superior to the properties of the commercial polyacrylate coating of comparative example 1.
Comparative example 3
A hardness performance test of a commercial polyacrylate coating comprises the following steps of
Taking an artificial board with the specification of 10cm x 10cm as a base material, brushing a commercial polyacrylate coating (model 22687 of Ji-nan Xin-sen chemical industry Co., ltd.) on the surface of the decorative paper, drying, and brushing a polyhydroxyacrylate coating on the surface of the artificial board for veneering hot pressing to finish the template preparation. A101-type Chinese hardness test pencil is used for testing the hardness of a paint film according to the national standard GB/T6739-2006, the test pencil with different hardness is sharpened and then treated by sand, then the pencil slides on a template at a constant speed of 1mm/s for 1cm at an angle of 45 degrees, the test is carried out successively from hard to soft, and the maximum pencil hardness without scratch is observed to be the hardness of the paint film of the tested template. The hardness of the commercial modified polyacrylate emulsion coating is H.
Comparative example 4
The hardness performance test of the easily cross-linked core-shell polyhydroxyacrylate emulsion comprises the following steps of
Taking an artificial board with the specification of 10cm x 10cm as a base material, brushing the core-shell type polyhydroxyacrylate emulsion in the embodiment 1 on the surface of decorative paper, drying, and then brushing the core-shell type polyhydroxyacrylate emulsion on the surface of the artificial board for veneering hot pressing (a test hot press (model is CREE-6014E-1), carrying out hot pressing for 5min at 130 ℃ under the pressure of 1.5-2.0 MPa), thereby completing the preparation of the template. The hardness of the coating film was measured by pencil test to be 2H. The coating film formed by the emulsion has good hardness performance.
According to the standard assessment of the cross-cut experiment of the color paint and varnish film of GB/T9286-1998, the adhesion performance of the examples is higher than that of the comparative examples, three functional groups of hydroxyl groups, carboxyl groups and epoxy groups introduced in the examples form a double cross-linking system, the reaction of the epoxy groups and the carboxyl groups in the polymerization process ensures the basic adhesive force of the polyhydroxyacrylate emulsion prepared in the examples, the secondary cross-linking of the hydroxyl groups and the epoxy groups in the polyhydroxyacrylate emulsion is realized through hot-pressing operation after the preparation is finished, and the hydroxyl peak and the epoxy peak in the polyhydroxyacrylate emulsion coating disappear and the adhesive force performance of the coating is enhanced as shown in the comparison before and after hot pressing in the figure 3; glycidyl methacrylate is introduced into the examples, the classification of the glycidyl methacrylate belongs to acrylate hard monomers, the effect of improving the hardness of the coating is achieved, and the hardness of the coating of the examples is evaluated to be superior to that of the comparative examples by the national standard GB/T6739-2006.
The above are only a few preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments. The particular embodiments disclosed above are illustrative only and not limiting as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein, wherein the modifications and improvements are made within the scope of the invention.
The invention is not a matter of the known technology.
Claims (3)
1. The preparation method of the easily cross-linked core-shell polyhydroxyacrylate emulsion coating is characterized by comprising the following steps of:
(1) Mixing the core layer monomer and the first emulsion, and stirring to obtain core layer pre-emulsion;
mixing the shell monomer with the second emulsion, and stirring to obtain a shell pre-emulsion;
in the nuclear layer pre-emulsion, the mass ratio is that the first emulsion: nuclear layer monomer= (2-3): (5-6);
in the shell layer pre-emulsion, the mass ratio is as follows: shell monomer= (2-3): (5-6);
the core layer monomer is a mixture of two or three of methyl methacrylate, butyl acrylate and glycidyl methacrylate, and the mass ratio of the methyl methacrylate is as follows: butyl acrylate: glycidyl methacrylate= (50-20): (0-20): (1-10); when the amount of the substance is 0, the substance is not added;
the shell monomer is a mixture of methyl methacrylate, butyl acrylate, acrylic acid and hydroxypropyl methacrylate, and the mass ratio of the methyl methacrylate is as follows: butyl acrylate: acrylic acid: hydroxypropyl methacrylate= (30-20): (30-20): (1-3): (1-8);
(2) Adding sodium bicarbonate and a third emulsion into a reactor, respectively dripping 25-35% by volume of nuclear layer pre-emulsion and 25-35% by volume of ammonium persulfate solution into the reactor for 15-20 min under the condition of nitrogen atmosphere and electromagnetic stirring at 75-80 ℃, keeping the reaction temperature at 75-80 ℃ and preserving the temperature for 0.5-1 h to form seed emulsion;
adding 0.5-1 g sodium bicarbonate into every 25-35 g third emulsion;
the first emulsion, the second emulsion and the third emulsion are the same in emulsifier, and are sodium dodecyl sulfate and OP-10 in mass ratio: OP-10=2: 1, a step of; the mass concentration of the first emulsion, the second emulsion and the third emulsion is the same or different and is 3 to 6 percent;
the mass ratio of the core layer pre-emulsion to the shell layer pre-emulsion is 1:0.9-1.1;
the mass ratio of the core layer pre-emulsion to the ammonium persulfate solution is (7-9): (1-1.5); the mass concentration of the ammonium persulfate solution is 0.10-0.18%;
the mass ratio of the first emulsion to the second emulsion to the third emulsion is 1:0.9-1.1:0.9-1.1;
(3) Then heating to 80-85 ℃, dropwise adding the nuclear layer pre-emulsion and 25-35% ammonium persulfate solution into the seed emulsion, and preserving heat for 0.5-1 h when the time is 1.5-1.75 h, thus finishing the nuclear layer preparation; then dropwise adding the shell pre-emulsion and the residual ammonium persulfate solution at the temperature of 80-85 ℃ for 2-2.25 h, carrying out heat preservation reaction for 0.5-1 h, then cooling to room temperature, and adjusting the pH value of the emulsion to 8-9 to obtain the easily cross-linked core-shell polyhydroxyacrylate emulsion coating;
the stirring speed in the step (1) is 1500-2000 r/min; the stirring time is 20-30 min.
2. The application of the easily cross-linked core-shell polyhydroxyacrylate emulsion coating prepared by the method according to claim 1, which is characterized by being applied to the surface coating of wood furniture.
3. The use according to claim 2, characterized in that it comprises in particular the following steps: the prepared core-shell type polyhydroxyacrylate emulsion is directly brushed on the front surface of the decorative paper, then dried in an oven at 120 ℃ for 30-60 s, taken out and placed at room temperature, the core-shell type polyhydroxyacrylate emulsion is brushed on the surface of the artificial board, the back surface of the decorative paper is attached to the artificial board, and hot pressing is carried out for 3-8 min under the conditions of 1.5-2.0 MPa and 120-160 ℃.
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| JPH0314856A (en) * | 1989-03-31 | 1991-01-23 | Takeda Chem Ind Ltd | Core-shell polymer |
| CN1800225A (en) * | 2005-12-28 | 2006-07-12 | 中国化工建设总公司常州涂料化工研究院 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
| CN102807648A (en) * | 2012-09-05 | 2012-12-05 | 陕西科技大学 | Method for preparing high-elasticity adhesive for fabric by adopting nuclear shell emulsion polymerization method |
| CN105777980A (en) * | 2016-05-16 | 2016-07-20 | 北京化工大学 | Epoxy/carboxyl-containing acrylate copolymer core-shell emulsion and preparation method and application thereof |
| CN107163180A (en) * | 2017-06-15 | 2017-09-15 | 陕西科技大学 | A kind of preparation method of anti-corrosion type core-shell polyacrylate emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0314856A (en) * | 1989-03-31 | 1991-01-23 | Takeda Chem Ind Ltd | Core-shell polymer |
| CN1800225A (en) * | 2005-12-28 | 2006-07-12 | 中国化工建设总公司常州涂料化工研究院 | Latex type hydroxy acryl acid resin possessing core-shell configuration |
| CN102807648A (en) * | 2012-09-05 | 2012-12-05 | 陕西科技大学 | Method for preparing high-elasticity adhesive for fabric by adopting nuclear shell emulsion polymerization method |
| CN105777980A (en) * | 2016-05-16 | 2016-07-20 | 北京化工大学 | Epoxy/carboxyl-containing acrylate copolymer core-shell emulsion and preparation method and application thereof |
| CN107163180A (en) * | 2017-06-15 | 2017-09-15 | 陕西科技大学 | A kind of preparation method of anti-corrosion type core-shell polyacrylate emulsion |
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