CN110804360A - APAO modified silicone-acrylic emulsion anti-sagging coating - Google Patents

APAO modified silicone-acrylic emulsion anti-sagging coating Download PDF

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Publication number
CN110804360A
CN110804360A CN201911137224.6A CN201911137224A CN110804360A CN 110804360 A CN110804360 A CN 110804360A CN 201911137224 A CN201911137224 A CN 201911137224A CN 110804360 A CN110804360 A CN 110804360A
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parts
apao
modified silicone
sagging
acrylic emulsion
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CN201911137224.6A
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张武
谢义鹏
康伦国
姚东生
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Shaoguan Union Chemical Co Ltd
Union Foshan Chemical Co Ltd
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Priority to CN201911137224.6A priority Critical patent/CN110804360A/en
Publication of CN110804360A publication Critical patent/CN110804360A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating 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
    • C09D151/06Coating 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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to an APAO modified silicone-acrylic emulsion anti-sagging paint which comprises the following components in parts by weight: 100.0-150.0 parts of APAO modified silicone-acrylic multifunctional emulsion, 20.0-30.0 parts of silicone-acrylic emulsion, 0.0-35.0 parts of pigment and filler, 1.0-7.0 parts of assistant, 3.0-6.0 parts of silane coupling agent, 4.0-7.0 parts of film-forming assistant and 10.0-40.0 parts of deionized water; the APAO modified silicone-acrylate multifunctional emulsion is prepared by reacting APAO, an acrylate hard monomer, an acrylate soft monomer, acrylic acid, organic silicon and a neutralizer; the APAO modified silicone-acrylic emulsion anti-sagging coating prepared by the invention has good adhesive force, anti-sagging property, fullness, wettability and other properties, is a good anti-sagging coating, and does not need an additional anti-sagging auxiliary agent when being applied to a slope or a vertical surface.

Description

APAO modified silicone-acrylic emulsion anti-sagging coating
Technical Field
The invention relates to a modified silicone-acrylate emulsion paint, in particular to an APAO modified silicone-acrylate emulsion anti-sagging paint, belonging to the technical field of water-based functional paints.
Background
At present, some large-scale projects, such as underground pipe galleries, large-scale system venue basement wall surfaces, subways, tunnels or civil air defense and the like, need to be constructed on vertical surfaces or slope surfaces, but the construction of the vertical surfaces or the slope surfaces is inconvenient, common coatings are easy to flow, the thickness is uneven, manual scraping is inconvenient, and the quality problem is easy to occur.
The existing coating used on the slope surface of a building has the phenomenon of sagging, and a filler with high density slowly sinks to cause the precipitation and delamination of the coating, thereby influencing the performance and normal use of the coating. At present, the coating is used as an anti-sagging agent in various types, such as organic bentonite, hydrogenated castor oil, polyamide wax, modified urea solution and the like, to improve the interface bonding of the filler and the prepolymer, so that the coating has thixotropic property, namely the viscosity of the coating is increased in the storage process, and the filler is prevented from precipitating; during construction, the viscosity of the coating is reduced when the coating is acted by external force, so that the construction is facilitated. However, the anti-sagging agent has a large addition amount, and needs to be activated before use, so that the production process is complicated and dust pollution is easily caused. The polyamide wax forms a network structure through hydrogen bonds, so that the viscosity of the product is increased, sagging is reduced, and the dispersibility and thixotropic effect of the polyamide wax are poor.
Chinese patent CN109868019A discloses a water-based spray coating with high anti-sagging performance, which comprises 6-13 parts of deionized water, 2-6 parts of organic alcohol, 0.3-2 parts of water-based dispersant, 0.2-1 part of alcohol amine, 0.1-0.3 part of defoaming agent, 3-20 parts of filler, 33-55 parts of water-based acrylic emulsion, 3-10 parts of amino resin, 0.1-0.8 part of thickener, 0.1-1 part of thixotropic agent and 0.1-3 parts of coating auxiliary agent.
Chinese patent CN109294428A discloses a single-component anti-sagging polyurethane waterproof coating, the raw materials of the waterproof coating comprise a polyurethane prepolymer, a thixotropic agent, a filler, a solvent and an auxiliary agent, the polyurethane prepolymer is prepared by the reaction of polyether polyol and first isocyanate, and the waterproof coating is characterized in that the thixotropic agent is formed by compounding modified nano calcium carbonate, polyurea and modified nano fumed silica, and the waterproof coating has excellent anti-sagging performance, physical and mechanical properties and waterproof performance;
the invention adopts the additional anti-sagging agent to achieve the anti-sagging effect of the coating, and the additional anti-sagging agent has a plurality of problems. Therefore, the anti-sagging coating which does not need to be added with the anti-sagging agent is developed, and the anti-sagging coating meets the requirements of the market and users and has wide market prospect.
Disclosure of Invention
In order to solve the technical problems, the invention overcomes the defects of a physically-added anti-sagging agent, and adopts APAO modified silicone-acrylic multifunctional emulsion with good anti-sagging performance as a main film forming substance of the coating, wherein the APAO is a low-molecular-weight amorphous plastomer material, and the microstructure of the APAO is in an amorphous and irregular arrangement state, so that the material has the characteristics which are not possessed by a plurality of crystalline polymers, the processing performance and the compatibility of the material can be effectively improved, the APAO has good viscosity, is not easy to migrate, has good anti-sagging performance, and also has good wetting performance.
The molecular structure of the silicone-acrylate emulsion is connected with the APAO through chemical bonds, so that the adhesive force and the anti-sagging performance of the silicone-acrylate emulsion can be effectively improved, and the silicone-acrylate emulsion is good in stability because of the chemical bond connection.
The invention aims to provide an APAO modified silicone-acrylic emulsion anti-sagging paint.
Another object of the present invention is to provide a method for preparing an APAO modified silicone-acrylic emulsion anti-sagging coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to an APAO modified silicone-acrylic emulsion anti-sagging paint and a preparation method thereof, wherein the APAO modified silicone-acrylic emulsion anti-sagging paint comprises the following components in parts by weight: 100.0-150.0 parts of APAO modified silicone-acrylic multifunctional emulsion, 20.0-30.0 parts of silicone-acrylic emulsion, 0.0-35.0 parts of pigment and filler, 1.0-7.0 parts of assistant, 3.0-6.0 parts of silane coupling agent, 4.0-7.0 parts of film-forming assistant and 10.0-40.0 parts of deionized water.
The pigment and filler is one or a combination of more of mica powder, barium sulfate, calcium carbonate, titanium dioxide and water-based nano color paste.
The auxiliary agent at least comprises one or a combination of a plurality of wetting agents, dispersing agents, defoaming agents, flatting agents, antifreezing agents, thickening agents, multifunctional auxiliary agents and nano auxiliary agents.
The film-forming assistant is one or a combination of more of propylene glycol butyl ether, propylene glycol methyl ether acetate and alcohol ester dodeca.
The APAO modified silicone-acrylate multifunctional emulsion comprises the following components in parts by weight: 2.0-5.0 parts of APAO, 24.0-48.0 parts of acrylate hard monomer, 6.0-16.0 parts of acrylate soft monomer, 10.0-20.0 parts of propylene glycol methyl ether acetate, 2.0-5.0 parts of acrylic acid, 1.0-3.0 parts of organic silicon, 0.1-0.3 part of azodiisobutyronitrile, 1.0-8.0 parts of neutralizer and 100.0-150.0 parts of deionized water.
Wherein the mass ratio of the hard acrylic monomer to the soft acrylic ester monomer is preferably 3.0-4.0: 1.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The acrylate hard monomer is one or a combination of methyl acrylate, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate and 2-propylheptyl acrylate.
The acrylate soft monomer is one or a combination of butyl acrylate, butyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl acrylate and glycidyl methacrylate.
The organic silicon is at least one of gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane and vinyl triisopropoxysilane; vinyl triisopropoxysilane is preferably employed; the addition amount of the organic silicon monomer accounts for 2.5-8% of the solid mass in the finally obtained APAO modified silicone-acrylic multifunctional emulsion.
The preparation method of the APAO modified silicone-acrylate multifunctional emulsion comprises the following steps:
1) in a storage tank, uniformly stirring 4/5 azodiisobutyronitrile, 1/3 propylene glycol monomethyl ether acetate, APAO, acrylic acid, organic silicon, an acrylic acid hard monomer and an acrylic acid soft monomer according to the weight part of the formula at normal temperature to obtain a mixed monomer I;
2) introducing nitrogen into the multifunctional reaction kettle, adding the remaining 2/3 propylene glycol monomethyl ether acetate, heating to 80-82 ℃, adding 1/4 of the mixed monomer I, stirring for reaction for 0.5-1.0 h until blue light appears, then dropwise adding the remaining mixed monomer I for 3.0-4.0 h, heating to 88-90 ℃ after dropwise adding is finished, adding the remaining 1/5 azodiisobutyronitrile, and carrying out heat preservation reaction for 1.0-1.5 h to finish the reaction;
3) cooling, adding a neutralizing agent, stirring at a high speed for dispersing for 0.5h, adding deionized water with the formula amount, stirring at a high speed for dispersing for 1.0h until the deionized water is completely dispersed, adding deionized water until the deionized water reaches a specified solid content, and filtering to obtain the APAO modified silicone-acrylate multifunctional emulsion.
The invention relates to APAO modified silicone-acrylate multifunctional emulsion, which is based on the patent of the invention and is described in detail.
Compared with the conventional silicone-acrylate emulsion coating, the APAO modified silicone-acrylate emulsion anti-sagging coating prepared by the invention has the following advantages:
1) the anti-sagging agent has good anti-sagging property, and does not need to be added with an anti-sagging auxiliary agent when being applied to a slope or a facade.
2) The APAO modified silicone-acrylate multifunctional emulsion is used as a main film forming substance, can effectively exert the characteristics of the APAO, has good adhesive force, sagging resistance, fullness, wettability and the like, and is a good sagging resistant coating.
Detailed Description
The invention is further described with reference to the following examples of an APAO modified silicone acrylic emulsion anti-sag coating and a method of making the same. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
An APAO modified silicone-acrylate multifunctional emulsion X comprises the following components in parts by weight: 3.0 parts of APAO, 35.0 parts of methyl methacrylate, 7.0 parts of butyl acrylate, 3.0 parts of lauryl methacrylate, 13.0 parts of propylene glycol methyl ether acetate, 3.5 parts of acrylic acid, 2.0 parts of vinyl triisopropoxy silane, 0.2 part of azobisisobutyronitrile, 4.0 parts of triethylamine and 110.0 parts of deionized water.
The preparation method of the APAO modified silicone-acrylate multifunctional emulsion X in the embodiment comprises the following steps:
1) in a storage tank, uniformly stirring 4/5 azodiisobutyronitrile, 1/3 propylene glycol monomethyl ether acetate, APAO, acrylic acid, vinyl triisopropoxysilane, methyl methacrylate, butyl acrylate and lauryl methacrylate according to the weight part of the formula at normal temperature to obtain a mixed monomer I;
2) introducing nitrogen into the multifunctional reaction kettle, adding the remaining 2/3 propylene glycol monomethyl ether acetate, heating to 80-82 ℃, adding 1/4 of the mixed monomer I, stirring for reaction for 1.0h until blue light appears, then dropwise adding the remaining mixed monomer I for 3.5h, heating to 88-90 ℃ after the dropwise adding is finished, adding the remaining 1/5 azodiisobutyronitrile, and carrying out heat preservation reaction for 1.5h to finish the reaction;
3) cooling, adding triethylamine, stirring at high speed for dispersing for 0.5h, adding deionized water with the formula amount, stirring at high speed for dispersing for 1.0h until the mixture is completely dispersed, adding deionized water until the mixture is regulated to the specified solid content, and filtering to obtain the APAO modified silicone-acrylic multifunctional emulsion X.
Example 2
An APAO modified silicone-acrylate multifunctional emulsion Y comprises the following components in parts by weight: 3.5 parts of APAO, 40.0 parts of isobornyl acrylate, 12.0 parts of glycidyl methacrylate, 17.0 parts of propylene glycol methyl ether acetate, 4.0 parts of acrylic acid, 2.5 parts of gamma-methacryloxypropyltrimethoxysilane, 0.2 part of azobisisobutyronitrile, 3.5 parts of ammonia water and 130.0 parts of deionized water.
The preparation method of the APAO modified silicone-acrylate multifunctional emulsion Y in the embodiment comprises the following steps:
1) in a storage tank, uniformly stirring 4/5 azodiisobutyronitrile, 1/3 propylene glycol monomethyl ether acetate, APAO, acrylic acid, gamma-methacryloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate according to the weight part of the formula at normal temperature to obtain a mixed monomer I;
2) introducing nitrogen into the multifunctional reaction kettle, adding the remaining 2/3 propylene glycol monomethyl ether acetate, heating to 80-82 ℃, adding 1/4 of the mixed monomer I, stirring for reaction for 1.0h until blue light appears, then dropwise adding the remaining mixed monomer I for 3.5h, heating to 88-90 ℃ after the dropwise adding is finished, adding the remaining 1/5 azodiisobutyronitrile, and carrying out heat preservation reaction for 1.5h to finish the reaction;
3) cooling, adding ammonia water, stirring at high speed for dispersing for 0.5h, adding deionized water with the formula amount, stirring at high speed for dispersing for 1.0h until the solution is completely dispersed, adding deionized water to the specified solid content, and filtering to obtain the APAO modified silicone-acrylic multifunctional emulsion Y.
Example 3
The APAO modified silicone-acrylic emulsion anti-sagging paint comprises the following components in parts by weight: 125.0 parts of APAO modified silicone-acrylic multifunctional emulsion X, 25.0 parts of silicone-acrylic emulsion, 8.0 parts of barium sulfate, 8.0 parts of titanium dioxide, 0.2 part of wetting agent, 0.8 part of dispersing agent, 0.5 part of defoaming agent, 0.3 part of flatting agent, 0.4 part of thickening agent, 0.6 part of multifunctional auxiliary agent, 4.0 parts of silane coupling agent, 3.0 parts of propylene glycol butyl ether, 3.0 parts of propylene glycol methyl ether acetate and 25.0 parts of deionized water.
Example 4
The APAO modified silicone-acrylic emulsion anti-sagging paint comprises the following components in parts by weight: 140.0 parts of APAO modified silicone-acrylic multifunctional emulsion Y, 28.0 parts of silicone-acrylic emulsion, 0.2 part of wetting agent, 0.2 part of defoaming agent, 0.4 part of flatting agent, 0.7 part of thickening agent, 5.0 parts of silane coupling agent, 6.0 parts of alcohol ester and 30.0 parts of deionized water.
The examples of the present invention were compared with conventional silicone-acrylic emulsion coatings according to performance index tests in accordance with the relevant standards of water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), salt fog resistance (GB/T1771-2007), impact resistance (GB/T1732-1993), pencil hardness (GB/T6739-1996), sag resistance (GB/T9264-2012), artificial aging resistance (GB/T14522), acid resistance ((10% HCl) GB/T1763-1979), alkali resistance ((10% NaOH) GB/1763-1979), and the like, and the performance indexes were as shown in Table 1.
TABLE 1 comparison of the properties of the examples with conventional silicone-acrylic emulsion coatings
Detecting items Example 3 Example 4 Comparative example
Water resistance 720h 720h 240h
Hardness of H H HB
Adhesion force Level 0 Level 0 Stage 2
Resistance to salt fog 800h 840h 240h
Impact resistance Is normal Is normal Cracking of paint film
Resistance to artificial aging 960h 1000h 240h
The storage stability is 50 +/-2 ℃/30d Is excellent in Is excellent in Little condensation
Alkali resistance 800h 800h 240h
Acid resistance 800h 820h 240h
Sag resistance Is excellent in Is excellent in Difference (D)
It can be seen from table 1 that the water resistance, salt spray resistance, artificial aging resistance, alkali resistance, acid resistance, adhesion, sag resistance, and the like of the example samples of the present invention far exceed those of the conventional silicone-acrylic emulsion coating.
The foregoing description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed; it will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.

Claims (4)

1. An APAO modified silicone-acrylic emulsion anti-sagging coating is characterized in that: the APAO modified silicone-acrylic emulsion anti-sagging paint comprises the following components in parts by weight: 100.0-150.0 parts of APAO modified silicone-acrylic multifunctional emulsion, 20.0-30.0 parts of silicone-acrylic emulsion, 0.0-35.0 parts of pigment and filler, 1.0-7.0 parts of assistant, 3.0-6.0 parts of silane coupling agent, 4.0-7.0 parts of film-forming assistant and 10.0-40.0 parts of deionized water;
the APAO modified silicone-acrylate multifunctional emulsion comprises the following components in parts by weight: 2.0-5.0 parts of APAO, 24.0-48.0 parts of acrylate hard monomer, 6.0-16.0 parts of acrylate soft monomer, 10.0-20.0 parts of propylene glycol methyl ether acetate, 2.0-5.0 parts of acrylic acid, 1.0-3.0 parts of organic silicon, 0.1-0.3 part of azodiisobutyronitrile, 1.0-8.0 parts of neutralizer and 100.0-150.0 parts of deionized water.
2. The APAO-modified silicone acrylic emulsion anti-sag coating of claim 1, wherein: the pigment and filler is one or a combination of more of mica powder, barium sulfate, calcium carbonate, titanium dioxide and water-based nano color paste.
3. The APAO-modified silicone acrylic emulsion anti-sag coating of claim 1, wherein: the auxiliary agent at least comprises one or a combination of a plurality of wetting agents, dispersing agents, defoaming agents, flatting agents, antifreezing agents, thickening agents, multifunctional auxiliary agents and nano auxiliary agents.
4. The APAO-modified silicone acrylic emulsion anti-sag coating of claim 1, wherein: the film-forming assistant is one or a combination of more of propylene glycol butyl ether, propylene glycol methyl ether acetate and alcohol ester dodeca.
CN201911137224.6A 2019-11-19 2019-11-19 APAO modified silicone-acrylic emulsion anti-sagging coating Pending CN110804360A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112940513A (en) * 2021-02-03 2021-06-11 湖南省升阳新材料有限公司 Anti-ultraviolet color master batch not prone to color change and preparation method thereof
CN115503320A (en) * 2022-09-26 2022-12-23 东莞市赛越新材料科技有限公司 Artificial imitation leather film and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101812263A (en) * 2010-04-16 2010-08-25 杭州美多乐化工有限公司 Waterborne weather-resistant self-cleaning type silicone acrylic latex paint and production method thereof
CN108102548A (en) * 2018-01-23 2018-06-01 中国铁路设计集团有限公司 A kind of high performance polymer asphalt waterproofing paint and preparation method thereof
CN108948921A (en) * 2018-06-29 2018-12-07 淮安市冰青建设工程管理有限公司 A kind of construction coating for internal wall that flexibility is good
CN110003393A (en) * 2019-04-26 2019-07-12 青岛创赢诺高分子材料有限责任公司 A kind of water-repellent preservation macromolecule emulsion and its production technology

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101812263A (en) * 2010-04-16 2010-08-25 杭州美多乐化工有限公司 Waterborne weather-resistant self-cleaning type silicone acrylic latex paint and production method thereof
CN108102548A (en) * 2018-01-23 2018-06-01 中国铁路设计集团有限公司 A kind of high performance polymer asphalt waterproofing paint and preparation method thereof
CN108948921A (en) * 2018-06-29 2018-12-07 淮安市冰青建设工程管理有限公司 A kind of construction coating for internal wall that flexibility is good
CN110003393A (en) * 2019-04-26 2019-07-12 青岛创赢诺高分子材料有限责任公司 A kind of water-repellent preservation macromolecule emulsion and its production technology

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112940513A (en) * 2021-02-03 2021-06-11 湖南省升阳新材料有限公司 Anti-ultraviolet color master batch not prone to color change and preparation method thereof
CN112940513B (en) * 2021-02-03 2022-06-17 湖南省升阳新材料有限公司 Anti-ultraviolet color master batch not prone to color change and preparation method thereof
CN115503320A (en) * 2022-09-26 2022-12-23 东莞市赛越新材料科技有限公司 Artificial imitation leather film and preparation method thereof

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Application publication date: 20200218