CN115124923A - Environment-friendly stone protective agent and preparation method thereof - Google Patents

Environment-friendly stone protective agent and preparation method thereof Download PDF

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Publication number
CN115124923A
CN115124923A CN202110987374.7A CN202110987374A CN115124923A CN 115124923 A CN115124923 A CN 115124923A CN 202110987374 A CN202110987374 A CN 202110987374A CN 115124923 A CN115124923 A CN 115124923A
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environment
parts
friendly stone
protective agent
alkyl siloxane
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CN202110987374.7A
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顾磊
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Shanghai Zuohang New Material Technology Co ltd
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Shanghai Zuohang New Material Technology Co ltd
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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
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • C09D183/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to C04B 41/49, and particularly relates to an environment-friendly stone protective agent and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 5-10 parts of silicate ester, 1-5 parts of alkyl siloxane, 5-10 parts of amino modified polysiloxane, 60-80 parts of solvent and 1-5 parts of assistant. The environment-friendly stone protective agent and the stone protective agent prepared by the preparation method provided by the invention have the advantages of excellent waterproof performance, acid and alkali resistance, excellent solvent resistance, good stability and excellent external resistance.

Description

Environment-friendly stone protective agent and preparation method thereof
Technical Field
The invention relates to C04B 41/49, and particularly relates to an environment-friendly stone protective agent and a preparation method thereof.
Background
The stone has the characteristics of excellent fire resistance, mechanical property and the like, and is widely applied to the field of buildings and the like. However, due to the influence of factors such as the structure of the stone (with capillary cracks) and the external environment (such as external liquid, rain water, oil stain) and the like, the stone is easy to generate water spots, bloom, rust and the like in the use process.
The patent CN201410038871.2 provides a novel oil-stain-resistant waterproof stone protective agent and a preparation method thereof, and the stone protective agent prepared by modified resin, modified silicone oil, alkyl alkoxy silane and the like has the capabilities of oil drainage, acid prevention and stain resistance.
The patent CN202010476955.X provides a maintenance-free and cracking-resistant stone protective agent for home decoration marble, which is prepared by blending organic silicon emulsion and acrylic ester and then adding modified bentonite for treatment, and can effectively prevent stone cracking.
Disclosure of Invention
In order to solve the technical problems, the invention provides an environment-friendly stone protective agent, which comprises the following raw materials in parts by weight: 5-10 parts of silicate ester, 1-5 parts of alkyl siloxane, 5-10 parts of amino modified polysiloxane, 60-80 parts of solvent and 1-5 parts of auxiliary agent.
Silicic acid ester
Preferably, the carbon chain length of the silicate ester is C1-8.
In order to further improve the impermeability and stability of the stone protective agent, the carbon chain length of the silicate ester is preferably C1-3. The silicate ester has lower molecular weight and better permeability, and is connected with the surface of the stone through the interaction between chemical bonds, so that the stone particles are reinforced and strengthened.
Preferably, the silicate comprises a first silicate and a second silicate. The mass ratio of the first silicate to the second silicate is (5-8): (1-3).
Alkyl siloxane
Preferably, the siloxane number of the alkyl siloxane is 2-4.
The invention unexpectedly discovers that alkyl siloxane in the stone protective agent plays an important role in permeating stones, and preferably comprises first alkyl siloxane and second alkyl siloxane in order to further improve the water resistance, acid and alkali resistance, impermeability and the like of the environment-friendly stone protective agent. The mass ratio of the first alkyl siloxane to the second alkyl siloxane is (8-12): (1-3).
Preferably, the carbon chain length of the first alkyl siloxane is C5 to C9.
Preferably, the carbon chain length of the second alkyl siloxane is C10-C16.
The stone protective agent prepared by the optimized alkyl siloxane has good water resistance and acid and alkali resistance, and the hydrophobicity is enhanced due to the synergy between the C5-C9 carbon chain alkyl siloxane and the C10-C16 carbon chain alkyl siloxane in the system, so that the mutual movement of molecular chain segments in the system is limited, and the stone protective force of the stone protective agent is increased.
Preferably, the mass ratio of the silicate ester to the alkyl siloxane is (15-17): (5-7).
Silicate ester is a multifunctional compound, and is easy to generate polycondensation reaction to cause cracking of the surface of the stone after film forming, so that the protection effect is not ideal. The research of the invention finds that the reaction is carried out by introducing alkyl siloxane into a system silicate ester, and particularly the mass ratio of the silicate ester to the alkyl siloxane is (15-17): and (5-7), the normal reaction is effectively prevented from being influenced by the overlarge steric hindrance, an organic silicon hydrophobic film is formed on the surface of the stone, the flexibility of the formed stone is improved, the defect of cracking of the stone is overcome, and the waterproof performance, acid and alkali resistance of the stone are improved.
Amino-modified polysiloxane
Preferably, the amino-modified polysiloxane includes a cyclic siloxane and an aminosilicone.
Preferably, the cyclic siloxane has the formula [ R 2 SiO]n, wherein R comprises-H and at least one of alkyl with chain length of C1-C3, and n is 1-8.
Preferably, the mass ratio of the total mass of the alkyl siloxane and the silicate ester to the amino silicone oil is (1-2): (1-2).
The invention has been found by unexpected researches that alkyl siloxane and silicate ester can remarkably improve the waterproof and stain-resistant properties of the material, and meanwhile, the addition of amino modified polysiloxane can effectively permeate stone pores, efficiently react and fill the stone with the help of an auxiliary agent, so that the compactness of the stone is improved, and the alkali substance migration is isolated under the condition of not influencing air permeability, thereby achieving the effect of alkali efflorescence resistance.
Solvent(s)
Preferably, the kinematic viscosity of the solvent at 40 ℃ is 1.2-1.5 mm 2 /s。
Preferably, the solvent includes a first solvent and a second solvent. The mass ratio of the first solvent to the second solvent is (5-8): (1-3).
Preferably, the flash point (closed end) of the first solvent is 45-50 ℃.
Preferably, the flash point (closed end) of the second solvent is 68-72 ℃.
Auxiliary agent
Preferably, the auxiliary agent comprises a catalyst and a silane coupling agent. The mass ratio of the catalyst to the silane coupling agent is (0.5-1): (2-5).
Preferably, the catalyst comprises at least one of dibutyltin dilaurate, azobisisobutyronitrile and octylamine.
Preferably, the silane coupling agent is a siloxane containing a glycidyl ether.
In order to further improve the performance of the environment-friendly stone protective agent, preferably, the mass ratio of the amino-modified polysiloxane to the silane coupling agent is (3-4): (1-2). The invention can reduce cracking of the stone, and can easily form organic and inorganic net structures, so that the stone protective agent is more tightly combined with the stone to form a tight stone protective film which is not easy to crack.
The second aspect of the invention provides a preparation method of an environment-friendly stone protective agent, which comprises the following steps: weighing the raw materials according to a formula, drying the raw materials in vacuum by using a vacuum drying device, sequentially adding a solvent, dispersing a coupling agent in a high-speed dispersing device uniformly, then continuously adding silicate ester, alkyl siloxane, cyclic siloxane and amino silicone oil, stirring and mixing uniformly, adding a catalyst, continuously stirring and reacting for 4-6 hours to obtain a mixture, drying the prepared mixture essential oil liquid by using a water absorption drying device, and filling the mixture into an automatic liquid filling device to obtain the environment-friendly stone protective agent.
Has the advantages that:
1) the environment-friendly stone protective agent and the stone protective agent prepared by the preparation method provided by the invention have excellent hydrophobicity, good waterproof performance, acid and alkali resistance and good solvent resistance.
2) The environment-friendly stone protective agent and the preparation method thereof provided by the invention have the advantages of good stability, good air permeability and excellent external resistance.
3) The environment-friendly stone protective agent and the stone protective agent prepared by the preparation method provided by the invention are wide in application range, and are particularly suitable for surface protection of marble materials.
Detailed Description
Examples
Example 1
An environment-friendly stone protective agent comprises the following raw materials in parts by weight: 8 parts of silicate ester, 3 parts of alkyl siloxane, 9 parts of amino modified polysiloxane, 70 parts of solvent and 4 parts of auxiliary agent.
The silicate comprises a first silicate and a second silicate. The mass ratio of the first silicate to the second silicate is 7: 2. the carbon chain length of the first silicate is C1, i.e. methyl silicate, type: and CG 501. The carbon chain length of the second silicate is C2, namely ethyl orthosilicate, type: and CG 502. The silicates were purchased from Jiangxi Chenguang New materials, Inc.
The alkyl siloxane has a siloxane number of 3. The alkylsiloxane includes a first alkylsiloxane and a second alkylsiloxane. The mass ratio of the first alkyl siloxane to the second alkyl siloxane is 10: 2. the carbon chain length of the first alkyl siloxane is C8, the first alkyl siloxane is n-octyl triethoxysilane, and the first alkyl siloxane is purchased from Shanghai Zonghang New Material science and technology Co., Ltd, model number: ZH-801. The second alkyl siloxane has a carbon chain length of C12, and the second alkyl siloxane is dodecyl trimethoxy silane available from caruncle morning photonics ltd, model number: CG-N1213.
The amino-modified polysiloxane includes cyclic siloxane and amino silicone oil. The cyclic siloxane has the formula [ R 2 SiO]n, wherein R is an alkyl group having a chain length of C, and n ═ 4, i.e., having the formula [ (CH) 3 ) 2 SiO] 4 . The amino-modified polysiloxane was purchased from besider chemical ltd, germany, type: MSI-1090.
The solvent includes a first solvent and a second solvent. The mass ratio of the first solvent to the second solvent is 7: 2. the kinematic viscosity of the first solvent at 40 ℃ is 1.30mm 2 And/s, the flash point (closed) is 47.1 ℃, and the first solvent is a hydrocarbon solvent D40. The kinematic viscosity of the second solvent at 40 ℃ is 1.47mm 2 (iv)/s, flash point (closed) 70.8 ℃, and the second solvent is hydrocarbon solvent D60. The solvents were purchased from Heizhou and ShilisiIndustrial limited company.
The auxiliary agent comprises a catalyst and a silane coupling agent. The mass ratio of the catalyst to the silane coupling agent is 0.8: 4.2.
the catalyst is dibutyltin dilaurate. The silane coupling agent is 3-glycidyl ether oxypropyltriethoxysilane (CAS number: 2602-34-8) available from Hubei Jusheng science and technology Co., Ltd.
A preparation method of an environment-friendly stone protective agent comprises the following steps: weighing the raw materials according to a formula, drying the raw materials in vacuum by using a vacuum drying device, sequentially adding a solvent, dispersing a coupling agent in a high-speed dispersing device uniformly, then continuously adding silicate ester, alkyl siloxane, cyclic siloxane and amino silicone oil, stirring and mixing uniformly, adding a catalyst, continuously stirring and reacting for 5 hours to obtain a mixture, drying the prepared mixture essential oil liquid water absorption drying device, introducing the dried mixture essential oil liquid into an automatic liquid filling device, and canning to obtain the environment-friendly stone protective agent.
Example 2
The specific implementation manner of the environment-friendly stone protective agent is the same as that in example 1, except that the mass ratio of the first alkyl siloxane to the second alkyl siloxane is 12: 3.
example 3
The specific implementation manner of the environment-friendly stone protective agent is the same as that in example 1, except that the mass ratio of the first silicate to the second silicate is 8: 3.
comparative example 1
The specific implementation manner of the environment-friendly stone protective agent is the same as that in example 1, except that the mass ratio of the first alkyl siloxane to the second alkyl siloxane is 6: 2.
comparative example 2
The specific implementation mode of the environment-friendly stone protective agent is the same as that in example 1, except that the raw materials comprise 8 parts of silicate ester, 4.5 parts of alkyl siloxane, 9 parts of amino modified polysiloxane, 70 parts of solvent and 4 parts of auxiliary agent.
Comparative example 3
The specific implementation mode of the environment-friendly stone protective agent is the same as that in example 1, except that the raw materials comprise 8 parts of silicate ester, 3 parts of alkyl siloxane, 5 parts of amino modified polysiloxane, 70 parts of solvent and 4 parts of auxiliary agent.
Performance testing
1. Testing the waterproofness; 2. testing acid and alkali resistance; 3. testing ultraviolet aging resistance; 4. impermeability; 5. and (5) testing the stability. The test was performed according to JC/T973-2005.
Table 1 results of performance testing
Figure BDA0003231210700000051

Claims (10)

1. The environment-friendly stone protective agent is characterized by comprising the following raw materials in parts by weight: 5-10 parts of silicate ester, 1-5 parts of alkyl siloxane, 5-10 parts of amino modified polysiloxane, 60-80 parts of solvent and 1-5 parts of auxiliary agent.
2. The environment-friendly stone protective agent as claimed in claim 1, wherein the carbon chain length of the silicate is from C1 to C8.
3. The environment-friendly stone protectant as claimed in claim 1, wherein the alkyl siloxane comprises a first alkyl siloxane and a second alkyl siloxane.
4. The environment-friendly stone protectant as claimed in claim 3, wherein the carbon chain length of the first alkyl siloxane is C5-C9.
5. The environment-friendly stone protective agent as claimed in claim 3, wherein the carbon chain length of the second alkyl siloxane is C10-C16.
6. The environment-friendly stone protectant according to claim 1, wherein the amino-modified polysiloxane comprises cyclic siloxane and amino silicone oil.
7. The environment-friendly stone protectant as claimed in claim 6, wherein the cyclic siloxane has a molecular formula of [ R [ ] 2 SiO]n, wherein R comprises-H and at least one of alkyl with chain length of C1-C3, and n is 1-8.
8. The environment-friendly stone protectant according to claim 1, wherein the kinematic viscosity of the solvent at 40 ℃ is 1.2-1.5.
9. The environment-friendly stone protectant as claimed in any one of claims 1 to 7, wherein the adjuvant includes a catalyst and a silane coupling agent.
10. The preparation method of the environment-friendly stone protective agent as claimed in claim 8 or 9, comprising the steps of: weighing the raw materials according to a formula, drying the raw materials in vacuum by using a vacuum drying device, sequentially adding a solvent, a coupling agent into a high-speed dispersing device for uniform dispersion, then continuously adding silicate ester, alkyl siloxane and amino modified polysiloxane, stirring and mixing the mixture uniformly, adding a catalyst, continuously stirring and reacting for 4 to 6 hours to obtain a mixture, drying the prepared mixture essential oil liquid water absorption drying device, introducing the dried mixture essential oil liquid into an automatic liquid filling device, and canning to obtain the environment-friendly stone protective agent.
CN202110987374.7A 2021-08-26 2021-08-26 Environment-friendly stone protective agent and preparation method thereof Pending CN115124923A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1506426A (en) * 2002-12-12 2004-06-23 曾繁杰 Prepn of stone material surface protecting agent
CN101358014A (en) * 2007-04-20 2009-02-04 赢创德固赛有限责任公司 Preparation containing organosilicium compound and its use
CN109777281A (en) * 2019-01-22 2019-05-21 雷洪金 A kind of stone protectant and preparation method thereof
CN111875411A (en) * 2020-07-07 2020-11-03 上海佐航新材料科技有限公司 Stone protective agent and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1506426A (en) * 2002-12-12 2004-06-23 曾繁杰 Prepn of stone material surface protecting agent
CN101358014A (en) * 2007-04-20 2009-02-04 赢创德固赛有限责任公司 Preparation containing organosilicium compound and its use
CN109777281A (en) * 2019-01-22 2019-05-21 雷洪金 A kind of stone protectant and preparation method thereof
CN111875411A (en) * 2020-07-07 2020-11-03 上海佐航新材料科技有限公司 Stone protective agent and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙顺杰等: "有机硅石材防护剂性能的研究", 《石材》 *

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Application publication date: 20220930