CN112538326B - Silane modified polyacrylate sealant and preparation method thereof - Google Patents

Silane modified polyacrylate sealant and preparation method thereof Download PDF

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CN112538326B
CN112538326B CN202011297457.5A CN202011297457A CN112538326B CN 112538326 B CN112538326 B CN 112538326B CN 202011297457 A CN202011297457 A CN 202011297457A CN 112538326 B CN112538326 B CN 112538326B
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modified polyacrylate
silane
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CN112538326A (en
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蒋凤娟
张斌
王海梅
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention provides a silane modified polyacrylate sealant and a preparation method thereof, wherein the silane modified sealant comprises the following components in parts by weight: 50-200 parts of silane modified polyacrylate, 50-200 parts of plasticizer, 100-300 parts of inorganic filler, 10-50 parts of thixotropic agent, 2-20 parts of water absorbent, 2-20 parts of adhesion promoter and 1-10 parts of catalyst. The silane modified polyacrylate sealant provided by the invention has the characteristics of high weather resistance, high strength, high elasticity and excellent adhesive force, and can be widely applied to the field of building and industrial sealing with higher requirement on weather resistance.

Description

Silane modified polyacrylate sealant and preparation method thereof
Technical Field
The invention belongs to the technical field of sealant bonding, and particularly relates to a silane modified polyacrylate sealant and a preparation method thereof.
Background
The silane modified sealant is a novel sealant which appears after the traditional silicone sealant, polyurethane sealant and polysulfide sealant. The silane modified sealant is originated from Japan at first, is widely applied to the field of construction, is promoted in Europe and North America successively, and is gradually expanded from the field of construction to a plurality of fields such as industrial assembly, traffic and the like.
The silane modified sealant reacts with water vapor in the air, siloxane groups in the polymer are hydrolyzed and crosslinked, and the silane modified sealant plays a role in bonding and sealing a bonding piece and is a moisture curing sealant. The silane modified sealant has the characteristics of both silicone and polyurethane sealant, and has excellent adhesion, weather resistance, oil resistance, coating property, environmental protection property and the like.
At present, silane modified sealants mainly comprise two types, namely silane modified polyether sealants and silane modified polyurethane sealants. The silane modified polyether sealant has excellent elasticity, low viscosity and convenient operation, but the polyether structure of the polymer main chain has insufficient weather resistance, and particularly has certain risk in the application of receiving sunlight for a long time outdoors. The silane modified polyurethane has higher cohesive strength, but the main chain structure of the polymer contains a urethane bond, so the problem of poor weather resistance also exists, and the general viscosity is higher, so the construction operation is influenced. In CN109135630A, polyacrylate containing siloxane groups is provided for preparing the sealant so as to improve the weather resistance of the sealant, the siloxane groups are randomly distributed on a main chain structure, the quantity is not controllable, the elasticity of the sealant is poor after crosslinking, the elongation at break is extremely low, the practical application of the sealant is limited, and the sealant has no universality. CN109503783A proposes a preparation method of a terminal siloxane modified polyacrylate block copolymer, but does not relate to the problem of how to improve the elasticity of polyacrylate and the adhesion of a sealant on a substrate.
Thus, there remains a need for new silane modified polyacrylate sealants that significantly improve the elasticity of polyacrylate sealants and their adhesion to substrates.
Disclosure of Invention
The invention aims to provide a silane modified polyacrylate sealant aiming at the problems of the existing silane modified sealant, and the silane modified polyacrylate sealant has the characteristics of high weather resistance, high strength, high elasticity and excellent adhesive force.
The invention also aims to provide a preparation method of the silane modified polyacrylate sealant.
In order to achieve the purpose, the invention adopts the following technical scheme:
the silane modified polyacrylate sealant comprises the following components in parts by weight: 50-200 parts of silane modified polyacrylate, 50-200 parts of plasticizer, 100-300 parts of inorganic filler, 10-50 parts of thixotropic agent, 2-20 parts of water absorbent, 2-20 parts of adhesion promoter and 1-10 parts of catalyst.
In a preferred embodiment, the silane modified polyacrylate sealant is composed of the following components in parts by weight: 100-150 parts of silane modified polyacrylate, 100-150 parts of plasticizer, 200-300 parts of inorganic filler, 20-40 parts of thixotropic agent, 5-10 parts of water absorbent, 5-10 parts of adhesion promoter and 2-5 parts of catalyst.
In one particular embodiment, the silane modified polyacrylate is a terminal siloxane modified polyacrylate prepared by atom transfer radical polymerization (AGET-ATRP) with an electron transfer generating catalyst and having the general structural formula:
Figure BDA0002785817080000031
wherein x is 0 or 1; m is any natural number of 100-500, preferably 200-500; n is any natural number of 10-200, preferably 20-100; s is any natural number of 1-10, preferably 2-7; t is any natural number of 10 to 200, preferably 20 to 100. R1，R2，R3Are the same or different C1-C10The substituted or unsubstituted aliphatic or aromatic linear or branched hydrocarbon group of (2) is preferably any of a methyl group, an ethyl group, a propyl group, a butylphenyl group and a benzyl group.
In a particular embodiment, the terminal siloxane is a siloxane containing 2 hydrolysable siloxane groups selected from one or more of trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl, methyldiethoxysilyl, preferably trimethoxysilyl or methyldimethoxysilyl. Specifically, the siloxane groups at two end groups in the structural general formula of the end group siloxane modified polyacrylate are selected from one or more of trimethoxysilyl, methyldimethoxysilyl, triethoxysilyl and methyldiethoxysilyl, and are preferably trimethoxysilyl or methyldimethoxysilyl.
In a specific embodiment, the plasticizer is phthalate or low molecular weight polyether, preferably one or more of low molecular weight polyether PPG1000, PPG2000, PPG 3000.
In a specific embodiment, the inorganic filler is one or more of heavy calcium carbonate, light calcium carbonate, talcum powder, kaolin, mica powder, titanium dioxide, carbon black and the like.
In a specific embodiment, the thixotropic agent is one or both of fumed silica or a polyamide wax.
In a specific embodiment, the water absorbent is vinyltrimethoxysilane.
In a specific embodiment, the adhesion promoter is one or more of gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-glycidylether aminomethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, and the like.
In a specific embodiment, the catalyst is one or two of stannous octoate, dibutyltin dilaurate and dibutyltin bis (acetylacetonate), preferably dibutyltin bis (acetylacetonate) with high catalytic efficiency.
In another aspect of the present invention, the preparation method of the silane modified polyacrylate sealant comprises the following steps:
1) preparing terminal siloxane modified polyacrylate by adopting an atom transfer radical polymerization method for generating a catalyst by electron transfer;
2) adding silane modified polyacrylate and a plasticizer in a certain weight proportion into a double-planet stirring kettle, uniformly stirring at room temperature, adding an inorganic filler and a thixotropic agent, uniformly stirring, heating to 110-120 ℃, and stirring in vacuum for 2-3 hours; and (3) reducing the water content to 1000ppm, then reducing the temperature to below 50 ℃, adding a water absorbent, an adhesion promoter and a catalyst, stirring for 0.5-1 hour in vacuum, and discharging.
Compared with the prior art, the invention has the advantages that:
1) according to the silane modified polyacrylate sealant provided by the invention, the polyethylene glycol flexible chain segment is introduced into the end group siloxane modified polyacrylate structure, so that the problem of poor elasticity of the silane modified acrylate sealant is solved, and the sealant with the characteristics of high weather resistance, high strength and high elasticity is obtained, so that the sealant has universality.
2) The silane modified polyacrylate sealant provided by the invention has a structure containing a large amount of polar groups such as hydroxyl, carboxyl and the like, so that the adhesive force to a base material is more excellent.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The silane modified polyacrylate sealant comprises the following components in parts by weight: 50-200 parts of silane modified polyacrylate, 50-200 parts of plasticizer, 100-300 parts of inorganic filler, 10-50 parts of thixotropic agent, 2-20 parts of water absorbent, 2-20 parts of adhesion promoter and 1-10 parts of catalyst.
Wherein the silane modified polyacrylate is terminal siloxane modified polyacrylate prepared by atom transfer radical polymerization (AGET-ATRP) of an electron transfer generation catalyst, and the structural general formula of the silane modified polyacrylate is as follows:
Figure BDA0002785817080000051
wherein x is 0 or 1; m is any natural number of 100-500, including but not limited to 100, 200, 300, 400, 500, preferably 200-300; n is any natural number of 10-200, including but not limited to 10, 30, 50, 80, 100, 160, 180, 200, preferably 20-100; s is any natural number from 1 to 10, and is selected from 1, 2,3, 4, 5, 6, 7, 8, 9 and 10, preferably from 2 to 7; t is any natural number from 10 to 200, including but not limited to 10, 30, 50, 80, 100, 160, 180, 200, preferably 20 to 100. R1，R2，R3Are the same or different C1-C10A substituted or unsubstituted aliphatic or aromatic straight-chain or branched-chain hydrocarbon group of (1), for exampleExamples thereof include methyl, ethyl, propyl, butyl and the like, and examples thereof include branched hydrocarbon groups such as isopropyl, 2-methylisobutyl and the like; the unsubstituted aromatic linear hydrocarbon group is, for example, a phenyl group, a benzyl group, a phenethyl group or the like, and the branched hydrocarbon group is, for example, an isobenzyl group, a diisophenethyl group; the substitution may be benzhydryl, and the like. R1，R2，R3Preferred are methyl, ethyl, propyl, butylphenyl, benzyl and the like, but not limited thereto. In the structural general formula of the terminal siloxane modified polyacrylate, m units represent conventional acrylate monomers, and n units represent acrylate monomers containing hydroxyl. When s is selected from 1-10, a polyethylene glycol flexible chain end is introduced into the silane polyacrylate polymer with the structure type, so that excellent elasticity is provided for the sealant on the basis of excellent weather resistance and bonding strength of the sealant, and meanwhile, the adhesive force to a base material is further improved by introducing polar groups such as hydroxyl, carboxyl and the like. Preferably, s is selected from 1 to 10, more preferably from 2 to 7.
The plasticizer used in the present invention is phthalate ester such as diisodecyl phthalate or low molecular weight polyether; the low molecular weight polyether generally has a molecular weight of 500-5000; preferably one or more of more environment-friendly low molecular weight polyether PPG1000, PPG2000, PPG3000 and the like; when a plurality of plasticizers are used, the plurality of plasticizers may be mixed in an arbitrary ratio, for example, average portion distribution and the like
The inorganic filler used in the invention is one or more of heavy calcium carbonate, light calcium carbonate, kaolin, talcum powder, mica powder, titanium dioxide, carbon black and the like; when the inorganic filler used is plural, the plural inorganic fillers may be mixed in an arbitrary ratio such as an average distribution and the like, and the particle size of the inorganic filler is not particularly limited, and is, for example, generally 50nm to 2 μm.
The thixotropic agent used in the invention is one or two of fumed silica or polyamide wax. When two thixotropic agents are used, the two thixotropic agents may be mixed in any ratio, for example, 1: 1 part, and the like.
The water-absorbing agent used in the present invention is vinyltrimethoxysilane which is more reactive with water.
The adhesion promoter used in the invention is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyl monoethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-glycidyl ether aminomethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and the like. When the adhesion promoter used is plural, the plural adhesion promoters may be mixed in an arbitrary ratio, for example, an average part ratio or the like.
The catalyst used in the invention is one or two of stannous octoate, dibutyltin dilaurate and dibutyltin bis (acetylacetonate), preferably dibutyltin bis (acetylacetonate) with high catalytic efficiency. When two catalysts are used, the two catalysts may be mixed in any ratio, for example 1: 1 part, and the like.
The method for preparing the silane modified polyacrylate sealant provided by the invention is to prepare the polyacrylate modified by the terminal siloxane at first and prepare the polyacrylate by adopting the atom transfer radical polymerization of the electron transfer generation catalyst, for example, refer to the patent CN109503783A previously applied by the inventor, and the relevant content of the polyacrylate modified by the terminal siloxane in the patent can be introduced into the invention. The terminal siloxane-modified polyacrylate preparation process of the present invention is made with reference to this prior patent, except where specifically noted.
Secondly, adding silane modified polyacrylate and a plasticizer into a double-planet stirring kettle according to the weight ratio of the components, uniformly stirring at room temperature, adding an inorganic filler and a thixotropic agent, uniformly stirring, heating to 110-120 ℃, and stirring in vacuum for 2-3 hours; and after the water content is qualified, cooling to below 50 ℃, adding a water absorbent, an adhesion promoter and a catalyst, stirring for 0.5-1 hour in vacuum, and discharging.
Wherein the stirring speed is not limited at all, for example, 60 rpm; the degree of vacuum of the vacuum agitation is not limited as long as the vacuum is applied, and is, for example, 5 kpa; whether the water content is qualified or not is detected according to a Karl Fischer volumetric method.
Preferably, the parts ratio of the components is as follows: 100-150 parts of silane modified polyacrylate, 100-150 parts of plasticizer, 200-300 parts of inorganic filler, 20-40 parts of thixotropic agent, 5-10 parts of water absorbent, 5-10 parts of adhesion promoter and 2-5 parts of catalyst. .
The preparation process according to the invention is further illustrated, without any limitation, by the following more specific examples.
The raw material sources are as follows:
the acrylate monomer is purchased from the group of Chinese medicines, carboxyl polyethylene glycol methacrylate 1-5 (molecular weight is 1000, 2000, 5000, 10000, 500 respectively) is purchased from Shanghai Tuo Yang biotechnology, and other reagents are purchased from Aladdin reagent;
PPG 2000: purchased from eastern bluestar, under the designation DL 2000;
heavy calcium carbonate: purchased from ultramicro lida under the designation LD 1000C;
light calcium carbonate: purchased from warner science and technology under the designation CCS 25;
titanium dioxide: purchased from dupont chemical, designation R902;
fumed silica: purchase from winning creative chemical industry, brand number R974;
a171: purchased from mai chart advanced materials;
a1120: purchased from mai chart advanced materials;
chelated tin catalyst: purchased from TIB chemical, designation C226;
silane-modified polyether: purchased from the brillouin chemical SH 303;
silane-modified polyurethane: purchased from map SPUR + 1050.
The test method comprises the following steps:
the tensile strength of the sealant is tested according to GB/T528-2009;
the elongation at break of the sealant is tested according to GB/T528-2009;
the peel strength of the sealant is tested according to GB/T13477;
the Shore hardness A of the sealant is tested according to GB-T2411-2008;
the weather resistance of the sealant is tested according to the standard JC-T485-2007 irradiation for 1000 hours.
Preparation example 1: self-made silane modified polyacrylate A
Firstly, 3 monomers of Butyl Acrylate (BA), Methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) are pretreated, an aluminum peroxide column is used for removing a polymerization inhibitor, and carboxyl polyethylene glycol methacrylate does not need to be treated. In a molar ratio n (mma): n (BA): n (HEMA): n (carboxy polyethylene glycol methacrylate 1) ═ 3:8:1:0.1, and an appropriate amount of initiator ethylene glycol dibromo isobutyrate (2-bromoisobutyrate) and triphenylphosphine (PPh)3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; and finally, removing transition metal ions by using an aluminum peroxide column as a polymerization product obtained by the reaction to obtain the polyacrylate A modified by the end group siloxane alkane.
Preparation example 2: self-made silane modified polyacrylate B
Firstly, Butyl Methacrylate (BMA), isooctyl acrylate (EHA) and hydroxyethyl methacrylate (HEMA)3 monomers are pretreated, an aluminum peroxide column is used for removing a polymerization inhibitor, and carboxyl polyethylene glycol methacrylate does not need to be treated. According to a molar ratio n (BMA): n (EHA): n (HEMA): n (carboxy polyethylene glycol methacrylate 2) ═ 3:2:1:0.1 was charged, and an appropriate amount of initiator Ethylene glycol dibromo isobutyrate (2-bromoisobutyrate) and triphenylphosphine (PPh)3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; and finally, removing transition metal ions by using an aluminum peroxide column as a polymerization product obtained by the reaction to obtain the polyacrylate B modified by the end group siloxane.
Preparation example 3: self-made silane modified polyacrylate C
Firstly, 3 monomers of Glycidyl Methacrylate (GMA), Butyl Acrylate (BA) and hydroxyethyl methacrylate (HEMA) are pretreated, an aluminum peroxide column is used for removing a polymerization inhibitor, and carboxyl polyethylene glycol methacrylate does not need to be treated. According to the molar ratio n (GMA): n (BA): n (HEMA): n (carboxy polyethylene glycol methacrylate 3) ═ 1:4:1:0.1 was charged, and an appropriate amount of initiator Ethylene glycol dibromo isobutyrate (2-bromoisobutyrate) and triphenylphosphine (PPh) were added3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethyleneebis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; and finally, removing transition metal ions by using an aluminum peroxide column as a polymerization product obtained by the reaction to obtain the polyacrylate C modified by the end group siloxane.
Preparation example 4: self-made silane modified polyacrylate D
Firstly, 3 monomers of Butyl Acrylate (BA), Methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) are pretreated, an aluminum peroxide column is used for removing a polymerization inhibitor, and carboxyl polyethylene glycol methacrylate does not need to be treatedAnd (6) processing. In a molar ratio n (mma): n (BA): n (HEMA): n (carboxy polyethylene glycol methacrylate 4) ═ 3:8:1:0.1 was charged, and an appropriate amount of initiator Ethylene glycol dibromo isobutyrate (2-bromoisobutyrate) and triphenylphosphine (PPh)3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 5L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; and finally, removing transition metal ions by using an aluminum peroxide column as a polymerization product obtained by the reaction to obtain the polyacrylate D modified by the end group siloxane.
Preparation example 5: self-made silane modified polyacrylate E
Firstly, 3 monomers of Butyl Acrylate (BA), Methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) are pretreated, an aluminum peroxide column is used for removing a polymerization inhibitor, and carboxyl polyethylene glycol methacrylate does not need to be treated. In a molar ratio n (mma): n (BA): n (HEMA): n (carboxy polyethylene glycol methacrylate 5) ═ 3:8:1:0.1, and an appropriate amount of initiator Ethylene glycol dibromo isobutyrate (2-bromoisobutyrate) and triphenylphosphine (PPh)3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; the reaction is most advancedAnd finally, removing transition metal ions from the obtained polymerization product through an aluminum peroxide column to obtain the end-group siloxane modified polyacrylate E.
Preparation example 6: self-made silane modified polyacrylate F
Firstly, Methyl Methacrylate (MMA), Butyl Acrylate (BA), isooctyl acrylate (EHA) and hydroxyethyl methacrylate (HEMA)4 monomers are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. In a molar ratio n (mma): n (BA): n (EHA): n (hema) 5:8:2:2 and the appropriate amount of initiator Ethylene glycol dibromoisobutyrate (2-bromoisobutyrate), triphenylphosphine (PPh)3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: and 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, carrying out oil bath reaction at the temperature of 80 ℃ for 6h, adding gamma-aminopropyltrimethoxysilane, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5h, quickly introducing air, and stopping the temperature reduction reaction; and finally, removing transition metal ions by using an aluminum peroxide column as a polymerization product obtained by the reaction to obtain the polyacrylate F modified by the end group siloxane.
Preparation example 7: self-made silane modified polyacrylate G
Firstly, Methyl Methacrylate (MMA), Butyl Acrylate (BA) and isooctyl acrylate (EHA)3 monomers are pretreated, and an aluminum peroxide column is used for removing a polymerization inhibitor. In a molar ratio n (mma): n (BA): n (EHA) is added in a ratio of 5:8:2, and a proper amount of initiator ethyl bromoisobutyrate and triphenylphosphine (PPh) are added3) Iron chloride hexahydrate (FeCl)3˙6H2O), Ethylene Glycol (EG), sodium bicarbonate (NaHCO)3) The feeding proportion is n (Ethylene bis (2-Bromoisobutyrate)): n (PPh)3)：n(FeCl3˙6H2O)：n(EG)：n(NaHCO3) 1: 1.2: 1: 1.5: 3, sequentially adding all reactants into a 2L single-neck flask, introducing nitrogen for 15min, sealing, and carrying out oil bath reaction at 80 DEG CAnd 6h, adding gamma-aminopropyl trimethoxy silane at the time, wherein the molar ratio of the added silane to the initiator ethylene glycol dibromoisobutyrate is 2.5: 1, continuously reacting for 0.5 h; rapidly introducing air, and stopping the temperature reduction reaction; removing transition metal ions from the obtained polymerization product through an aluminum peroxide column to obtain the silane modified polyacrylate G.
The feed proportion of the preparation example is as follows:
Figure BDA0002785817080000131
Figure BDA0002785817080000141
example 1
Adding 120 parts of self-made silane modified polyacrylate A and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 2
Adding 200 parts of self-made silane modified polyacrylate A and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 3
Adding 50 parts of self-made silane modified polyacrylate A and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 4
Adding 120 parts of self-made silane modified polyacrylate B and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 5
Adding 120 parts of self-made silane modified polyacrylate C and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 6
Adding 120 parts of self-made silane modified polyacrylate A and 150 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 100 parts of heavy calcium carbonate, 150 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 7
Adding 120 parts of self-made silane modified polyacrylate A and 180 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 120 parts of heavy calcium carbonate, 120 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 8
Adding 120 parts of self-made silane modified polyacrylate D and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Example 9
Adding 120 parts of self-made silane modified polyacrylate E and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Comparative example 1
Adding silane modified polyether SH 303120 parts and PPG2000 plasticizer 120 parts into a double-planet stirring kettle, uniformly stirring at room temperature, adding heavy calcium carbonate 60 parts, light calcium carbonate 180 parts, titanium dioxide 5 parts and fumed silica 30 parts, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Comparative example 2
Adding silane modified polyurethane SPUR + 1050120 parts and PPG2000 plasticizer 120 parts into a double-planet stirring kettle, uniformly stirring at room temperature, adding ground calcium carbonate 60 parts, light calcium carbonate 180 parts, titanium dioxide 5 parts and fumed silica 30 parts, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Comparative example 3
Adding 120 parts of self-made silane modified polyacrylate F and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
Comparative example 4
Adding 120 parts of self-made silane modified polyacrylate G and 120 parts of PPG2000 plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding 60 parts of heavy calcium carbonate, 180 parts of light calcium carbonate, 5 parts of titanium dioxide and 30 parts of fumed silica, uniformly stirring, heating to 110 ℃, and stirring in vacuum for 2 hours; testing the water content of the paste to be less than 1000ppm, cooling to below 50 ℃, adding 7 parts of A171 water absorbent, 8 parts of A1120 silane coupling agent and 3 parts of chelated tin catalyst, stirring for 0.5 hour in vacuum, and discharging.
The prepared sealant is prepared into test sample strips and test pieces according to the relevant standards, and the test standards are as follows: the sealant comprises the following main components and performance test results of tensile strength (GB/T528-2009), elongation at break (GB/T528-2009), peel strength (GB/T13477) and shore hardness A (GB-T2411-2008), and is irradiated for 1000 hours in a weather resistance experiment according to a standard JC-T485-2007:
Figure BDA0002785817080000181
from the above results, the weather resistance of the silane modified polyacrylate sealant of the embodiments 1 to 9 is greatly improved compared with the silane modified polyether sealant of the comparative example 1 and the silane modified polyurethane sealant of the comparative example 2, and the strength retention rate is over 85% after the ultraviolet irradiation for 1000 hours, which is much higher than that of the comparative examples 1 and 2; compared with the comparative examples 3 and 4, the introduction of the polyethylene glycol flexible chain segment greatly improves the elongation at break of the sealant, and the elasticity is excellent; compared with the comparative examples 3 and 4, the examples 1-9 also introduce a large amount of hydroxyl and carboxyl polar groups simultaneously, the peel strength reaches cohesive failure of more than 90%, and the adhesive force of the sealant to the base material is greatly improved. The silane modified polyacrylate sealant provided by the invention has the characteristics of high weather resistance, high strength, high elasticity and excellent adhesive force, and can be widely applied to the field of building and industrial sealing with higher requirement on weather resistance.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (14)

1. The silane modified polyacrylate sealant is characterized by comprising the following components in parts by weight: 50-200 parts of silane modified polyacrylate, 50-200 parts of plasticizer, 100-300 parts of inorganic filler, 10-50 parts of thixotropic agent, 2-20 parts of water absorbent, 2-20 parts of adhesion promoter and 1-10 parts of catalyst;
the silane modified polyacrylate is terminal siloxane modified polyacrylate prepared by atom transfer radical polymerization (AGET-ATRP) of an electron transfer generation catalyst, and the structural general formula of the terminal siloxane modified polyacrylate is as follows:
Figure FDA0003454513370000011
wherein x is 0 or 1; m is any natural number of 100-500; n is any natural number of 10-200; s is any natural number of 1-10; t is any natural number of 10 to 200, R1，R2，R3Are the same or different C1-C10Substituted or unsubstituted aliphatic or aromatic straight or branched hydrocarbon group.
2. The silane modified polyacrylate sealant according to claim 1, which is composed of the following components in parts by weight: 100-150 parts of silane modified polyacrylate, 100-150 parts of plasticizer, 200-300 parts of inorganic filler, 20-40 parts of thixotropic agent, 5-10 parts of water absorbent, 5-10 parts of adhesion promoter and 2-5 parts of catalyst.
3. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein in the general structural formula, x is 0 or 1; m is any natural number of 200-300; n is any natural number of 20-100; s is any natural number of 2-7; t is any natural number of 20-100, R1，R2，R3Is any one of methyl, ethyl, propyl, butylphenyl and benzyl.
4. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein the terminal siloxane is a siloxane group containing 2 hydrolyzable groups selected from one or more of trimethoxysilyl group, methyldimethoxysilyl group, triethoxysilyl group, and methyldiethoxysilyl group.
5. The silane-modified polyacrylate sealant according to claim 4, wherein the hydrolyzable siloxane group is trimethoxysilyl group or methyldimethoxysilyl group.
6. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein the plasticizer is a phthalate or a low molecular weight polyether.
7. The silane modified polyacrylate sealant of claim 6 wherein the plasticizer is one or more of low molecular weight polyether PPG1000, PPG2000, PPG 3000.
8. The silane modified polyacrylate sealant according to claim 1 or 2, wherein the inorganic filler is one or more of heavy calcium carbonate, light calcium carbonate, talc, kaolin, mica powder, titanium dioxide and carbon black.
9. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein the thixotropic agent is one or both of fumed silica and polyamide wax.
10. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein the water absorbent is vinyltrimethoxysilane.
11. The silane modified polyacrylate sealant according to claim 1 or 2, wherein the adhesion promoter is one or more of γ -aminopropyltriethoxysilane, γ -aminopropylmethoxyethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -glycidioxyetheraminomethoxysilane, γ -acryloxypropyltrimethoxysilane, γ - (2, 3-glycidoxy) propyltrimethoxysilane.
12. The silane-modified polyacrylate sealant according to claim 1 or 2, wherein the catalyst is one or two of stannous octoate, dibutyltin dilaurate and dibutyltin bis (acetylacetonate).
13. The silane-modified polyacrylate sealant according to claim 12, wherein the catalyst is dibutyltin bis (acetylacetonate).
14. The process for preparing a silane modified polyacrylate sealant according to any one of claims 1 to 13, comprising the steps of:
1) preparing terminal siloxane modified polyacrylate by adopting an atom transfer radical polymerization method for generating a catalyst by electron transfer;
2) adding silane modified polyacrylate and a plasticizer into a double-planet stirring kettle, uniformly stirring at room temperature, adding an inorganic filler and a thixotropic agent, uniformly stirring, heating to 110-120 ℃, and stirring in vacuum for 2-3 hours; and (3) reducing the water content to 1000ppm, then reducing the temperature to below 50 ℃, adding a water absorbent, an adhesion promoter and a catalyst, stirring for 0.5-1 hour in vacuum, and discharging.
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