CN112851868B - Self-repairing emulsion with core-shell structure and preparation method and application thereof - Google Patents
Self-repairing emulsion with core-shell structure and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a self-repairing emulsion with a core-shell structure, a preparation method and an application thereof, wherein the emulsion is prepared from the following components in parts by mass: 4.5-7.5 parts of an emulsifier; 8-13 parts of a soft monomer; 28-44 parts of hard monomer; 1.1-2.3 parts of acrylic acid; 1.5-4 parts of N-butoxy methacrylamide; 1.5-4 parts of ethylene urea ethoxy methacrylate; 1-2 parts of acrylonitrile; 3.5-7.5 parts of thermal initiator; 45-55 parts of water. According to the invention, a large number of N-H bonds and CN bonds with high polarity are introduced to have self-repairing capability, and the resin has a low film-forming temperature under the condition of a high glass transition temperature, so that the contamination resistance and scrubbing resistance of the coating can be greatly improved.
Description
Technical Field
The invention relates to a self-repairing emulsion, in particular to a self-repairing emulsion with a core-shell structure, a preparation method and application thereof, belonging to the field of coatings.
Background
After the conventional exterior wall flat coating paint is applied, the appearance changes such as shrinkage and expansion of a wall substrate along with the changes of service life and external temperature often cause cracks on a continuous and compact paint film of the common exterior wall flat coating paint, and the appearance is affected. In order to solve the problem, a layer of elastic coating with certain tensile property is generally applied to resist the deformation of the wall base material and cover cracks; however, the glass transition temperature of the resin used for maintaining the performance of the elastic coating is usually low, which leads to the characteristics of softness and viscosity of the elastic coating, poor stain resistance, contamination of the outer wall coating surface with a large amount of impurities such as dust and the like along with the lapse of time, difficulty in cleaning after the paint film is contaminated, and the wall is mottled and unattractive after the paint film is contaminated for a long time. Therefore, an acrylic emulsion having a self-repairing function to resist deformation of a wall substrate, prevent a paint film from cracking, and having a good stain resistance is needed.
The common self-repairing coating at present mainly takes polyurethane emulsion and acrylate emulsion synthesized by multiple hydrogen bond monomers as main materials, the polyurethane emulsion and the acrylate emulsion have a large number of reversible hydrogen bonds, and when a paint film cracks, the cracks are repaired through the action of the hydrogen bonds, so that the resins at the two ends of the cracks are connected again. However, the existing polyurethane emulsion is expensive, multiple hydrogen bond monomers are difficult to industrialize, and the performance price is low, so that most market demands cannot be met. Therefore, it is necessary to develop an emulsion coating which is inexpensive and has a self-repairing function.
Disclosure of Invention
The invention aims to provide an acrylic emulsion with a self-repairing function and low price, which has the function of repairing paint film cracks by adjusting a core-shell structure, and has good film forming property, excellent stain resistance and excellent scrubbing resistance.
Another object of the present invention is to provide a method for preparing a self-repairing emulsion and its application.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the self-repairing emulsion with the core-shell structure is prepared from the following components in parts by mass:
4.5-7.5 parts of an emulsifier;
8-13 parts of a soft monomer;
28-44 parts of hard monomer;
1.1-2.3 parts of acrylic acid;
1.5-4 parts of N-butoxy methacrylamide;
1.5-4 parts of ethylene urea ethoxy methacrylate;
1-2 parts of acrylonitrile;
3.5-7.5 parts of thermal initiator;
45-55 parts of water.
Further, the emulsion consists of a core layer structure and a shell layer structure; wherein the preparation process of the nuclear layer structure comprises a kettle bottom solution A, a pre-emulsion B1 and a thermal initiator C1, and the shell layer comprises a pre-emulsion B2 and a thermal initiator solution C2;
the kettle bottom liquid A comprises: 5-10 parts of water and 0.3-3 parts of emulsifier;
the pre-emulsion B1 comprises: 14-25 parts of water, 0.5-3.5 parts of emulsifier, 2-7 parts of soft monomer, 20-35 parts of hard monomer and 0.5-1.5 parts of acrylic acid;
the thermal initiator solution C1 includes: 0.1-5 parts of thermal initiator and 3-6 parts of water;
the pre-emulsion B2 comprises: 10-20 parts of water, 0.5-3.5 parts of emulsifier, 3-9 parts of soft monomer, 8-15 parts of hard monomer, 0.1-1.5 parts of acrylic acid, 1-2 parts of acrylonitrile, 1.5-4 parts of N-butoxy methacrylamide and 1.5-4 parts of ethylene urea ethoxy methacrylate;
the thermal initiator solution C2 includes: 0.1-4 parts of thermal initiator and 3.5-6 parts of water.
Further, the emulsifier is an anionic emulsifier or a reactive nonionic emulsifier;
preferably, the anionic emulsifier comprises at least one of carboxylate sodium oleate, sodium abietate, sodium naphthenate, sodium ricinoleate, synthetic fatty acid sodium soap, sodium dodecyl sulfate alkyl sulfate, sodium alkyl sulfonate and sodium alkyl benzene sulfonate;
preferably, the nonionic emulsifier includes at least one of allylic polyoxyethylene ether, allylic nonylphenol polyoxyethylene ether, allyloxy polyoxyethylene ether, acrylamide polyoxyethylene ether, styrene polyoxyethylene ether, (meth) acrylic polyoxyethylene ether, and maleate polyoxyethylene ether, more preferably allylic nonylphenol polyoxyethylene ether and/or styrene polyoxyethylene ether.
Further, the thermal initiator comprises one or more of peroxide, reductant and persulfate thermal initiator, preferably ammonium persulfate and sodium persulfate.
Further, the soft monomer is an acrylic monomer with a single double bond and a glass transition temperature below 0 ℃, and preferably one or more of butyl acrylate, isooctyl acrylate and ethyl acrylate.
Further, the hard monomer is an acrylic monomer containing a single double bond and having a glass transition temperature of more than 0 ℃, preferably one or more of styrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl methacrylate and n-butyl methacrylate; more preferably one or more of styrene, methyl acrylate and methyl methacrylate.
A method for preparing the self-repairing emulsion with the core-shell structure comprises the following steps:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device;
b. adding the pre-emulsion B1 into the first pre-emulsion tank, and uniformly stirring and mixing for later use;
c. adding a thermal initiator solution C1 into the thermal initiator tank I;
d. adding the pre-emulsion B2 into the second pre-emulsion, and stirring and mixing uniformly for later use;
e. adding a thermal initiator solution C2 into the thermal initiator tank II;
f. when the temperature in the polymerization kettle reaches 75-85 ℃, adding 10-20% of pre-emulsion B1 and 10-20% of thermal initiator solution C1 into the kettle, and then, simultaneously dropwise adding the rest pre-emulsion B1 and thermal initiator solution C1 into the polymerization kettle; when the pre-emulsion B1 and the C1 are added in dropwise, preserving the heat for 0.5 to 2 hours, continuously and synchronously adding the pre-emulsion B2 and the thermal initiator solution C2 in dropwise, and preserving the heat for 0.5 to 2 hours after the dropwise addition is finished;
g. controlling the temperature in the polymerization kettle to be 20-55 ℃, adding a neutralizing agent to adjust the pH value of the emulsion to be neutral, filtering and discharging to obtain the emulsion.
Preferably, the neutralizer is one or more of ammonia, organic amine, sodium hydroxide and sodium carbonate, preferably one or more of ammonia, sodium hydroxide and sodium carbonate.
The self-repairing emulsion is applied to the fields of coatings, adhesives or textiles, and is preferably used for preparing exterior wall flat coating coatings.
The emulsion of the invention has the following beneficial effects:
1. according to the invention, a large number of N-H bonds and CN bonds with high polarity can be introduced into the acrylic emulsion, so that a large number of hydrogen bonds are formed; the self-repairing capability is achieved by the fracture and formation of hydrogen bonds under the normal temperature condition. Compared with the traditional self-repairing polyurethane emulsion, the self-repairing emulsion has lower cost, the raw material monomer is convenient to obtain, and the industrialization is easier to realize.
2. The invention adopts a core-shell structure with distributed specific functional groups, more functional groups for realizing the self-repairing function are distributed on the surface of the latex particles, the contact area is increased, and the self-repairing capability is further improved.
3. The N-butoxymethyl acrylamide and the ethylene urea ethoxy methacrylate functional monomer used in the invention can also improve the film forming performance of the emulsion, and realize that the resin has lower film forming temperature under the condition of higher glass transition temperature, thereby greatly improving the stain resistance and scrubbing resistance of the coating.
4. Can form the synergistic application of hydrogen bond monomers, and can further improve the adhesive force between a paint film and a base material, so that the paint film has excellent scrubbing resistance.
5. The N-H bond and the CN bond of the emulsion are distributed on the surface of the emulsion particle, so that the contact area with a substrate is increased, more hydrogen bonds are formed, and the scrubbing resistance of the coating is further improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of the invention and not limiting of its scope.
The main raw material information in the examples is as follows:
SDS (sodium dodecyl sulfate): sodium dodecyl sulfate, Jiangsu Haian petrochemical
And (3) SDBS: sodium dodecyl benzene sulfonate, Jiangsu Haian petrochemical
OP-10: alkylphenol polyoxyethylene ether, Jiangsu Haian petrochemical
AA: acrylic acid, Beijing Oriental chemical plant
NIBMA: n-butoxymethylacrylamide, Sanwang chemical materials, Guangzhou
MEEU: ethylene Urea Ethoxymethacrylate, Hubei Xinming chemical Co., Ltd
AN: acrylonitrile, Att New Material Co Ltd
BA: butyl acrylate, Beijing Oriental chemical plant
2-EHA: isooctyl acrylate, Beijing Oriental chemical plant
EA: ethyl acrylate, Beijing Oriental chemical plant
MMA: methyl methacrylate, Beijing Oriental chemical plant
MA: methyl acrylate, Beijing Oriental chemical plant
St: styrene, Beijing Oriental chemical plant
APS: ammonium persulfate, Tianjin Zhentai chemical Co., Ltd
[ example 1 ]
Self-repairing emulsion with a core-shell structure is prepared according to the raw material composition and the dosage in the table 1 and the following steps:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device;
b. adding the pre-emulsion B1 into the first pre-emulsion tank, and uniformly stirring and mixing for later use;
c. adding a thermal initiator solution C1 into the thermal initiator tank I;
d. adding the pre-emulsion B2 into the second pre-emulsion, and stirring and mixing uniformly for later use;
e. adding a thermal initiator solution C2 into a thermal initiator tank II;
f. when the temperature in the polymerization kettle reaches 80 ℃, adding 10% of pre-emulsion B1 and 10% of thermal initiator solution C1 into the kettle, and then, dropwise adding the rest of pre-emulsion B1 and thermal initiator solution C1 into the polymerization kettle; when the pre-emulsion B1 and the C1 are added in a dropwise manner, preserving the heat for 0.5h, continuously and synchronously adding the pre-emulsion B2 and the thermal initiator solution C2 in a dropwise manner, and controlling the total dropwise adding time of the step f to be 180 min; after the dropwise adding is finished, preserving the heat for 1 h;
g. and (3) controlling the temperature in the polymerization kettle to be reduced to normal temperature, adding ammonia water to adjust the pH value of the emulsion to be 7, filtering and discharging to obtain the emulsion.
Emulsion formulations in Table 1, examples 1-5
[ examples 2 to 5 ]
Self-healing emulsions were prepared according to the raw material compositions in table 1, with other operating conditions and in the same manner as in example 1.
Comparative example 1
The acrylic emulsion for the flat coating with the high glass transition temperature and without the core-shell structure is prepared according to the following steps:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device; the kettle bottom liquid A comprises: 20 kg of water and 2.8 kg of SDS.
b. Adding the pre-emulsion B into an emulsion tank, and uniformly stirring and mixing for later use; the pre-emulsion B comprises: 32 kg of water, 2 kg of SDS, 13 kg of BA, 44 kg of MMA and 2 kg of AA.
c. Adding a thermal initiator solution C into a thermal initiator tank; the thermal initiator solution C includes: APS 3 kg, water 5 kg.
d. When the temperature in the polymerization kettle reaches 80 ℃, adding 10% of pre-emulsion B and 10% of thermal initiator solution C into the kettle, then, dropwise adding the rest pre-emulsion B and thermal initiator solution C into the polymerization kettle simultaneously, controlling the total dropwise adding time of the step d to be 180min, and after the dropwise adding is finished, preserving the temperature for 1 h;
e. and (3) controlling the temperature in the polymerization kettle to be reduced to normal temperature, adding ammonia water to adjust the pH value of the emulsion to 7, filtering and discharging to obtain the emulsion.
Comparative example 2
The acrylic emulsion for ordinary flat coating without a core-shell structure was prepared as follows:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device; the kettle bottom liquid A comprises: 18 kg of water, 1 kg of SDS.
b. Adding the pre-emulsion B into an emulsion tank, and uniformly stirring and mixing for later use; the pre-emulsion B comprises: 30 kg of water, 1.5 kg of SDS, 20 kg of BA, 40 kg of MMA and 5 kg of AA.
c. Adding a thermal initiator solution C into a thermal initiator tank; the thermal initiator solution C includes: 5 kg of APS and 5 kg of water.
d. When the temperature in the polymerization kettle reaches 82 ℃, adding 10% of pre-emulsion B and 10% of thermal initiator solution C into the kettle, then, simultaneously dropwise adding the rest pre-emulsion B and thermal initiator solution C into the polymerization kettle, controlling the total dropwise adding time in the step d to be 180 minutes, and after the dropwise adding is finished, keeping the temperature for 1 hour;
e. and (3) controlling the temperature in the polymerization kettle to be reduced to normal temperature, adding ammonia water to adjust the pH value of the emulsion to 7, filtering and discharging to obtain the emulsion.
Comparative example 3
The acrylic emulsion for flat coating with a core-shell structure was prepared as follows:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device;
b. adding the pre-emulsion B1 into the first pre-emulsion tank, and uniformly stirring and mixing for later use;
c. adding a thermal initiator solution C1 into the thermal initiator tank I;
d. adding the pre-emulsion B2 into the second pre-emulsion, and stirring and mixing uniformly for later use;
e. adding a thermal initiator solution C2 into a thermal initiator tank II;
f. when the temperature in the polymerization kettle reaches 80 ℃, adding 10% of pre-emulsion B1 and 10% of thermal initiator solution C1 into the kettle, and then, dropwise adding the rest of pre-emulsion B1 and thermal initiator solution C1 into the polymerization kettle; when the pre-emulsion B1 and the C1 are dripped, preserving the heat for 0.5h, continuously and synchronously dripping the pre-emulsion B2 and the thermal initiator solution C2, and controlling the total dripping time of the step f to be 180 min; after the dropwise adding is finished, preserving the heat for 1 h;
g. and (3) controlling the temperature in the polymerization kettle to be reduced to normal temperature, adding ammonia water to adjust the pH value of the emulsion to be 7, filtering and discharging to obtain the emulsion.
And (3) testing the performance of the coating: the coatings were formulated according to the following formulation in table 2;
TABLE 2 test coating formulations
Glass transition temperature test method: an appropriate amount of the emulsion is removed, the mixture is dried in an oven at 150 ℃ for 4 hours, and the resin is taken out and tested for glass transition temperature by using an HS-DSC-101 glass transition temperature tester.
Film forming temperature test method: coating the emulsion on an MFFT-60/MFFT-90 film-forming temperature test instrument by using a 100-micron rod type coating device, and observing the highest temperature of a continuous cracking position after the emulsion is dried to form a film, wherein the highest temperature is the film-forming temperature;
the stain resistance test method comprises the following steps: GB/T9755-.
The scrub resistance test method comprises the following steps: GB/T9755-.
The self-repairing performance test method comprises the following steps: a layer of even paint film is coated on a PVC substrate with a substrate of 0.9mm by a 100-micron wire rod, 3 paint films are prepared for each product, the product is maintained for 7 days in a constant-temperature and constant-humidity environment with the temperature of 25 +/-1 ℃ and the humidity of 50 +/-5 percent, a performance test is carried out, and after the product is brushed for 25 times by a copper brush, the trace recovery time is tested.
The specific indexes and detection values of the emulsion prepared in each example and comparative example are shown in the following table 3:
TABLE 3 Performance index of the coatings
As can be seen from the above test results, the method of the present invention (examples 1-5) can prepare acrylic emulsions with higher glass transition temperature (Tg), and has the following advantages compared with the techniques of comparative examples 1-3:
(1) the emulsions prepared in examples 1-5 had much lower film forming temperatures and therefore better film forming properties than comparative example 1, which also had a higher Tg;
(2) compared with the conventional prior art comparative example 2 with low Tg, the emulsions prepared in examples 1 to 5 have more excellent scrubbing resistance, stain resistance and self-repairing capability on the premise that the film forming temperature is equivalent to that of the emulsion prepared in the prior art comparative example 2;
(3) compared with comparative example 3 which has a core-shell structure and higher Tg, the emulsions prepared in examples 1 to 5 have better scrubbing resistance, stain resistance and self-repairing capability on the premise that the film forming temperature is equivalent to that of the emulsion prepared in comparative example 3, and show that the emulsion for exterior wall flat coating with excellent performance can be prepared.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (16)
1. The self-repairing emulsion with the core-shell structure is characterized by consisting of a core-layer structure and a shell-layer structure; wherein the preparation process of the nuclear layer structure comprises a kettle bottom solution A, a pre-emulsion B1 and a thermal initiator C1, and the shell layer comprises a pre-emulsion B2 and a thermal initiator solution C2; according to the mass portion of the raw materials,
the kettle bottom liquid A comprises: 5-10 parts of water and 0.3-3 parts of emulsifier;
the pre-emulsion B1 comprises: 14-25 parts of water, 0.5-3.5 parts of emulsifier, 2-7 parts of soft monomer, 20-35 parts of hard monomer and 0.5-1.5 parts of acrylic acid;
the thermal initiator solution C1 includes: 0.1-5 parts of thermal initiator and 3-6 parts of water;
the pre-emulsion B2 comprises: 10-20 parts of water, 0.5-3.5 parts of emulsifier, 3-9 parts of soft monomer, 8-15 parts of hard monomer, 0.1-1.5 parts of acrylic acid, 1-2 parts of acrylonitrile, 1.5-4 parts of N-butoxy methacrylamide and 1.5-4 parts of ethylene urea ethoxy methacrylate;
the thermal initiator solution C2 includes: 0.1-4 parts of thermal initiator and 3.5-6 parts of water;
the preparation method of the self-repairing emulsion comprises the following steps:
a. adding the kettle bottom liquid A into a polymerization kettle with a stirring device, a condenser and a peristaltic pump feeding device;
b. adding the pre-emulsion B1 into the first pre-emulsion tank, and uniformly stirring and mixing for later use;
c. adding a thermal initiator solution C1 into the thermal initiator tank I;
d. adding the pre-emulsion B2 into the second pre-emulsion, and stirring and mixing uniformly for later use;
e. adding a thermal initiator solution C2 into a thermal initiator tank II;
f. when the temperature in the polymerization kettle reaches 75-85 ℃, adding 10-20% of pre-emulsion B1 and 10-20% of thermal initiator solution C1 into the kettle, and then, dropwise adding the rest of pre-emulsion B1 and thermal initiator solution C1 into the polymerization kettle; when the pre-emulsion B1 and the C1 are added in dropwise, preserving the heat for 0.5 to 2 hours, continuously and synchronously adding the pre-emulsion B2 and the thermal initiator solution C2 in dropwise, and preserving the heat for 0.5 to 2 hours after the dropwise addition is finished;
g. controlling the temperature in the polymerization kettle to be 20-55 ℃, adding a neutralizing agent to adjust the pH value of the emulsion to be neutral, filtering and discharging to obtain the emulsion.
2. The self-repairing emulsion of core-shell structure according to claim 1, wherein said emulsifier is an anionic emulsifier or a reactive nonionic emulsifier.
3. The self-repairing emulsion of core-shell structure according to claim 2, wherein said anionic emulsifier comprises at least one of carboxylate type sodium oleate, sodium abietate, sodium naphthenate, sodium ricinoleate, synthetic fatty acid sodium soap, sodium dodecyl sulfate alkyl sulfate, sodium alkyl sulfonate, and sodium alkyl benzene sulfonate.
4. The core-shell structured self-repairing emulsion according to claim 2, wherein said nonionic emulsifier comprises at least one of allylpolyoxyethylene ether, allylnonylphenol polyoxyethylene ether, allyloxy polyoxyethylene ether, acrylamide polyoxyethylene ether, styrene polyoxyethylene ether, (meth) acrylic polyoxyethylene ether, and maleate polyoxyethylene ether.
5. The self-repairing emulsion with a core-shell structure according to claim 4, wherein the non-ionic emulsifier is selected from allyl polyoxyethylene nonylphenol ether and/or styrene polyoxyethylene ether.
6. The core-shell structured self-healing emulsion according to claim 2, wherein said thermal initiator comprises one or more of a peroxide, a reductant, and a persulfate thermal initiator.
7. The self-repairing emulsion with a core-shell structure according to claim 6, wherein the thermal initiator is selected from ammonium persulfate and sodium persulfate.
8. The self-healing emulsion of core-shell structure according to any of claims 1 to 7, wherein said soft monomer is an acrylic monomer having a single double bond and a glass transition temperature below 0 ℃.
9. The self-repairing emulsion with a core-shell structure according to claim 8, wherein the soft monomer is one or more of butyl acrylate, isooctyl acrylate and ethyl acrylate.
10. The self-repairing emulsion with a core-shell structure according to any one of claims 1-7, wherein the hard monomer is an acrylic monomer with a single double bond and a glass transition temperature above 0 ℃.
11. The self-repairing emulsion with a core-shell structure according to claim 10, wherein the hard monomer is one or more of styrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl methacrylate and n-butyl methacrylate.
12. The self-repairing emulsion with a core-shell structure according to claim 10, wherein the hard monomer is one or more of styrene, methyl acrylate and methyl methacrylate.
13. The self-repairing emulsion with a core-shell structure according to claim 1, wherein the neutralizing agent is one or more of ammonia water, organic amine, sodium hydroxide and sodium carbonate.
14. The core-shell structured self-healing emulsion according to claim 2, wherein the neutralizing agent is one or more of ammonia, sodium hydroxide, sodium carbonate.
15. A self-healing emulsion according to any one of claims 1 to 14 for use in coatings, adhesives or textiles.
16. The self-repairing emulsion of any one of claims 1-14 applied to the preparation of exterior wall flat coating paint.
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