CN108752590B - Long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, modified inorganic silicate coating thereof and preparation method thereof - Google Patents

Long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, modified inorganic silicate coating thereof and preparation method thereof Download PDF

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CN108752590B
CN108752590B CN201810378067.7A CN201810378067A CN108752590B CN 108752590 B CN108752590 B CN 108752590B CN 201810378067 A CN201810378067 A CN 201810378067A CN 108752590 B CN108752590 B CN 108752590B
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刘伟区
江驰
王政芳
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Zhongke Testing Technology Service Guangzhou Co ltd
Zhongke Guanghua Chongqing New Material Research Institute Co ltd
University of Chinese Academy of Sciences
Guangzhou Chemical Co Ltd of CAS
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    • C09D1/02Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract

The invention belongs to the technical field of coating preparation, and discloses a long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, a modified inorganic silicate coating thereof and a preparation method thereof. The long-chain silicon-oxygen-based fluorine-containing siloxane emulsion modified inorganic silicate coating comprises the following components in parts by weight: 100 parts of inorganic silicate solution; 2-30 parts of long-chain siloxane-based fluorine-containing siloxane emulsion; 10-50 parts of water; 0.5-4 parts of a defoaming agent; 0.5-4 parts of a dispersing agent; 0.1-4 parts of a leveling agent; 100-200 parts of filler. The invention also discloses a preparation method of the composition. The inorganic silicate coating can adopt the processes of rolling coating, spraying, brushing and the like, has a surface contact angle of 100-145 degrees, is water-resistant and acid-alkali-resistant, has no abnormality in alkali resistance for 48 hours, is resistant to washing (no bottom exposure for 1200 times), effectively prevents the problems of cracking, falling, powder falling and the like of the coating in the using process, and has wide application in the fields of high-hydrophobicity and high-antifouling building interior and exterior walls.

Description

Long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, modified inorganic silicate coating thereof and preparation method thereof
Technical Field
The invention belongs to the field of inorganic silicate coatings, and particularly relates to a long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, a modified inorganic silicate coating thereof and a preparation method thereof.
Background
At present, inorganic silicate is used as a film forming material in commercially available inorganic silicate coatings, and meanwhile, the inorganic silicate has the advantages of rich raw material sources, high temperature resistance, aging resistance, no pollution and the like, and meets the requirements of energy conservation and environmental protection of modern building materials. Although the inorganic silicate paint has many advantages, as the coating has many fine holes, dust, organic matters and the like on the surface of a building are continuously deposited along with the prolonging of the service time, which greatly reduces the decorative effect of the paint. And with the development of urban high-rise buildings, the existence of pollutants brings negative influence to the cleaning of the buildings. All this has affected the large-scale application of inorganic silicate coatings.
Functional chain segments such as organic silicon, organic fluorine and the like are introduced into the inorganic silicate coating, and Si-O bonds and C-F bonds with larger bond energy are introduced into molecules, so that the surface energy of the coating can be greatly reduced, and the coating is endowed with high waterproof, high antifouling and other performances. Common organosilicon and organofluorine monomers containing reactive functional groups are mainly silane coupling agents. The inorganic silicate coating modified by the organosilicon or organofluorosilane coupling agent has the following defects, such as short molecular chain and unobvious modification effect; and hydrolytic groups in the silane coupling agent have high activity and are easy to react with each other to generate crosslinking entanglement, so that the stability of the silane coupling agent is poor. If the inorganic silicate coating is modified by physically mixing both the organosilicon and the organofluorine, the compatibility is poor. Therefore, if a long-chain silicone segment and a fluorine-containing group can be simultaneously introduced into the bulk structure of the modified product, the compatibility between the two and the modification effect thereof can be improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a long-chain siloxane-based fluorine-containing siloxane emulsion and a preparation method thereof. The invention also aims to provide the inorganic silicate coating modified by the long-chain silicon-oxygen-based fluorine-containing siloxane emulsion and the preparation method thereof.
The purpose of the invention is realized by the following scheme:
a long-chain siloxy fluorine-containing siloxane emulsion has a chemical structural formula shown as a formula I:
Figure BDA0001640333570000021
wherein R is1、R2Is methylalkoxy, ethylalkoxy, hydroxy or
Figure BDA0001640333570000022
RfIs a fluorine-containing alkyl group having 1 to 8 carbon atoms, n1、n2Is a natural number which can be divided by 4 in 4-2000.
Preferably, the emulsion has a solids content of 20% to 50%.
A preparation method of long-chain siloxy fluorine-containing siloxane emulsion comprises the following steps of adding 80-160 parts of water, 2-6 parts of anionic emulsifier, 2-4 parts of nonionic emulsifier and 6-40 parts of octamethylcyclotetrasiloxane into a reactor, reacting for 4-10h at 60-90 ℃ under the protection of nitrogen, adding 10-40 parts of micromolecular fluorine-containing siloxane, and reacting for 2-10h at 65-90 ℃ to obtain the long-chain siloxy fluorine-containing siloxane emulsion.
Preferably, the anionic emulsifier is at least one of dodecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid or octadecylbenzene sulfonic acid.
Preferably, the nonionic emulsifier is at least one of alkylphenol polyoxyethylene ether, polyoxyethylene alkyl ether or polyoxyethylene sorbitan stearate.
Preferably, the small molecule fluorine-containing siloxane is at least one of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
The long-chain silicon-oxygen-based fluorine-containing siloxane emulsion modified inorganic silicate coating comprises the following components in parts by weight:
Figure BDA0001640333570000031
preferably, the inorganic silicate solution has a modulus of 1.0 to 6.0 of a sodium silicate aqueous solution and/or a modulus of 1.0 to 6.0 of a potassium silicate aqueous solution.
Preferably, the defoaming agent refers to mineral oil defoaming agents and/or polysiloxane defoaming agents; the dispersant is at least one of acrylate, carboxylic acid sodium salt or polyacrylate; the leveling agent is an acrylic leveling agent; the filler is at least one of titanium dioxide, silicon dioxide or light calcium carbonate.
A preparation method of a long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating comprises the following steps: adding inorganic silicate solution, water and long-chain siloxy fluorine-containing siloxane emulsion into a reactor, and uniformly stirring; and then adding a defoaming agent, a dispersing agent and a flatting agent, stirring uniformly, then adding a filler, and dispersing at normal temperature for 3-12h, and uniformly to obtain the long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating.
The mechanism of the invention is as follows:
the long-chain silicon-oxygen-containing fluorine-containing siloxane emulsion used by the invention effectively migrates to the surface of a coating by simultaneously introducing the long-chain organic silicon and the fluorine-containing group, and improves the water resistance and the stain resistance of the coating, so that the prepared coating not only has weather resistance, water resistance and acid and alkali resistance, but also can solve the problems of cracking, falling, powder falling and the like of the coating in construction, and has excellent high hydrophobicity and high antifouling property.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention firstly prepares a long-chain silicon-oxygen-based fluorine-containing siloxane emulsion by emulsion polymerization, then further hybridizes with inorganic silicate to obtain a hybrid solution with high hydrophobic property, and develops a high hydrophobic and high antifouling inorganic silicate coating by using the hybrid solution as a main film forming substance.
(2) The inorganic silicate coating modified by the long-chain siloxy fluorine-containing siloxane emulsion contains long-chain organosilicon and fluorine-containing groups, and the fluorine-containing groups migrate to the surface of a coating in the coating film forming process, so that the contact angle (100-145 degrees) of the surface of the coating is effectively improved, and the prepared inorganic silicate coating has high hydrophobic and high antifouling effects.
(3) The long-chain siloxane-containing fluorine-containing silicone emulsion modified inorganic silicate coating has the advantages of water resistance, acid and alkali resistance, no abnormality in alkali resistance for 48 hours, washing resistance (no bottom exposure for 1200 times), and capability of effectively preventing the problems of cracking, falling, powder falling and the like of the coating.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparation of long-chain siloxy fluorine-containing siloxane emulsion
Adding 80g of deionized water, 2g of dodecylbenzene sulfonic acid, 2g of alkylphenol polyoxyethylene ether and 10g of octamethylcyclotetrasiloxane into a reaction container provided with a thermometer, a stirrer, a condenser and nitrogen, reacting at 70 ℃ for 9 hours, adding 15g of trifluoropropyltrimethoxysilane, reacting at 75 ℃ for 9 hours, and then air-cooling and discharging to obtain the long-chain siloxy fluorine-containing siloxane emulsion with the solid content of 26%.
(2) Preparation of long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating
Adding 100 parts by weight of sodium silicate aqueous solution with the modulus of 2, 10 parts by weight of water and 4 parts by weight of long-chain silicon-oxygen-based fluorine-containing siloxane emulsion into a reaction kettle at one time, and uniformly stirring; then adding 0.5 weight part of mineral oil defoaming agent, 0.5 weight part of acrylate dispersing agent and 0.2 weight part of acrylic flatting agent, stirring uniformly, then adding 100 weight parts of light calcium carbonate, dispersing for 3 hours at normal temperature, and dispersing uniformly to obtain the inorganic silicate coating.
The coating was applied by a spray coater and tested for properties according to JGT 26-2002. The test results were as follows: the surface drying time is 1.8 h; construction performance: coating the second channel without obstacles; the appearance of the coating film is normal; the alkali resistance is not abnormal within 48 hours; washing and brushing resistance: no bottom exposure occurs for 2000 times; contrast ratio: 0.94, the stain resistance is 4 percent (less than or equal to 15 percent, which reaches the II-grade standard in JGT 26-2002), the contact angle is as follows: 105 deg..
Example 2
(1) Preparation of long-chain siloxy fluorine-containing siloxane emulsion
100g of deionized water, 4g of hexadecylbenzene sulfonic acid, 3g of polyoxyethylene alkyl ether and 20g of octamethylcyclotetrasiloxane are added into a reaction container provided with a thermometer, a stirrer, a condenser pipe and nitrogen, the mixture reacts for 6 hours at 80 ℃, 10g of hexafluorobutyl propyl trimethoxy silane is added, the mixture reacts for 4 hours at 80 ℃, and then air cooling and discharging are carried out, so that long-chain siloxane-based fluorine-containing siloxane emulsion is obtained, wherein the solid content is 27%.
(2) Preparation of long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating
Adding 100 parts by weight of potassium silicate water solution with the modulus of 3, 20 parts by weight of water and 10 parts by weight of long-chain silicon-oxygen-based fluorine-containing siloxane emulsion into a reaction kettle at one time, and uniformly stirring; then adding 1 weight part of polysiloxane defoaming agent, 1 weight part of polyacrylate dispersant and 1.5 weight parts of acrylic flatting agent, stirring uniformly, then adding 150 weight parts of silicon dioxide, dispersing for 4 hours at normal temperature, and dispersing uniformly to obtain the inorganic silicate coating.
The coating was applied by a spray coater and tested for properties according to JGT 26-2002. The test results were as follows: surface drying time is 1.5 h; construction performance: coating the second channel without obstacles; the appearance of the coating film is normal; the alkali resistance is not abnormal within 48 hours; washing and brushing resistance: no bottom exposure occurs for 2000 times; contrast ratio: 0.96, the stain resistance is 3.5 percent (less than or equal to 15 percent, which reaches the II-grade standard in JGT 26-2002), the contact angle is as follows: 125 deg.
Example 3
(1) Preparation of long-chain siloxy fluorine-containing siloxane emulsion
Adding 120g of deionized water, 5g of hexadecylbenzene sulfonic acid, 4g of polyoxyethylene alkyl ether and 40g of octamethylcyclotetrasiloxane into a reaction container provided with a thermometer, a stirrer, a condenser pipe and nitrogen, reacting for 4 hours at 90 ℃, then adding 20g of heptadecafluorodecyltrimethoxysilane, reacting for 2 hours at 90 ℃, and then performing air cooling discharging to obtain the long-chain siloxy fluorine-containing siloxane emulsion with the solid content of 36%.
(2) Preparation of long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating
Adding 100 parts by weight of potassium silicate aqueous solution with the modulus of 6, 50 parts by weight of water and 30 parts by weight of long-chain silicon-oxygen-based fluorine-containing siloxane emulsion into a reaction kettle at one time, and uniformly stirring; and then adding 4 parts by weight of mineral oil defoaming agent, 3 parts by weight of acrylate dispersing agent and 4 parts by weight of acrylic flatting agent, stirring uniformly, then adding 200 parts by weight of titanium dioxide, dispersing at normal temperature for 12 hours, and dispersing uniformly to obtain the inorganic silicate coating.
The coating was applied by a spray coater and tested for properties according to JGT 26-2002. The test results were as follows: surface drying time is 1.2 h; construction performance: coating the second channel without obstacles; the appearance of the coating film is normal; the alkali resistance is not abnormal within 48 hours; washing and brushing resistance: no bottom exposure occurs for 2000 times; contrast ratio: 0.98, the stain resistance is 2 percent (less than or equal to 15 percent, which reaches the II-grade standard in JGT 26-2002), the contact angle is as follows: 145 deg..
Example 4
(1) Preparation of long-chain siloxy fluorine-containing siloxane emulsion
100g of deionized water, 4g of octadecyl benzene sulfonic acid, 3g of polyoxyethylene sorbitan stearate and 30g of octamethylcyclotetrasiloxane are added into a reaction container provided with a thermometer, a stirrer, a condenser and nitrogen, the mixture reacts for 8 hours at 75 ℃, 15g of trifluoropropyltrimethoxysilane and 10g of dodecafluoroheptyl propyltrimethoxysilane are added, the mixture reacts for 6 hours at 75 ℃, and then air cooling and discharging are carried out to obtain the long-chain siloxy fluorine-containing siloxane emulsion, wherein the solid content is 38%.
(2) Preparation of long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating
Adding 50 parts by weight of a sodium silicate aqueous solution with a modulus of 4, 50 parts by weight of a sodium silicate aqueous solution with a modulus of 6, 30 parts by weight of water and 20 parts by weight of long-chain silicon-oxygen-based fluorine-containing siloxane emulsion into a reaction kettle at one time, and uniformly stirring; and then adding 1 part by weight of mineral oil defoaming agent, 2 parts by weight of polysiloxane defoaming agent, 2 parts by weight of acrylate dispersing agent and 2 parts by weight of acrylic flatting agent, stirring uniformly, then adding 100 parts by weight of titanium dioxide and 50 parts by weight of silicon dioxide, dispersing at normal temperature for 6 hours, and dispersing uniformly to obtain the inorganic silicate coating.
The coating was applied by a spray coater and tested for properties according to JGT 26-2002. The test results were as follows: surface drying time is 1.5 h; construction performance: coating the second channel without obstacles; the appearance of the coating film is normal; the alkali resistance is not abnormal within 48 hours; washing and brushing resistance: no bottom exposure occurs for 2000 times; contrast ratio: 0.96, the stain resistance is 3 percent (less than or equal to 15 percent, which reaches the II-grade standard in JGT 26-2002), the contact angle is as follows: 135 deg.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. The long-chain silicon-oxygen-based fluorine-containing siloxane emulsion modified inorganic silicate coating is characterized by comprising the following components in parts by weight:
Figure FDA0002959167290000011
the preparation method of the long-chain siloxy fluorine-containing siloxane emulsion comprises the following steps: adding 80-160 parts of water, 2-6 parts of anionic emulsifier, 2-4 parts of nonionic emulsifier and 6-40 parts of octamethylcyclotetrasiloxane into a reactor, reacting at 60-90 ℃ for 4-10h under the protection of nitrogen, adding 10-40 parts of micromolecular fluorine-containing siloxane, and reacting at 65-90 ℃ for 2-10h to obtain the long-chain silicon-oxygen-based fluorine-containing siloxane emulsion.
2. The coating of claim 1, wherein the anionic emulsifier is at least one of dodecylbenzene sulfonic acid, hexadecylbenzene sulfonic acid, or octadecylbenzene sulfonic acid.
3. The coating of claim 1, wherein the non-ionic emulsifier is at least one of an alkylphenol polyoxyethylene ether, a polyoxyethylene alkyl ether, or a polyoxyethylene sorbitan stearate.
4. The coating of claim 1, wherein the small molecule fluorosilicone is at least one of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hexafluorobutylpropyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane.
5. The coating according to claim 1, wherein the inorganic silicate solution has an aqueous solution of sodium silicate having a modulus of 1.0 to 6.0 and/or an aqueous solution of potassium silicate having a modulus of 1.0 to 6.0.
6. The coating according to claim 1, wherein the defoaming agent is mineral oil type defoaming agent and/or polysiloxane type defoaming agent; the dispersant is at least one of acrylate, carboxylic acid sodium salt or polyacrylate; the leveling agent is an acrylic leveling agent; the filler is at least one of titanium dioxide, silicon dioxide or light calcium carbonate.
7. The method for preparing the long-chain siloxy and fluorosilicone emulsion modified inorganic silicate coating of any one of claims 1 to 6, comprising the steps of: adding inorganic silicate solution, water and long-chain siloxy fluorine-containing siloxane emulsion into a reactor, and uniformly stirring; and then adding a defoaming agent, a dispersing agent and a flatting agent, stirring uniformly, then adding a filler, and dispersing at normal temperature for 3-12h, and uniformly to obtain the long-chain siloxy fluorine-containing siloxane emulsion modified inorganic silicate coating.
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"有机硅、氟高分子表面活性剂在建材中的应用发展";黄月文,等;《高分子通报》;20050630(第3期);第89-95页 *

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