Acrylate modified MS resin and its preparation method and application in MS sealant

Abstract

The present invention belongs to the technical field of sealants, and specifically relates to an acrylate-modified MS resin, a preparation method thereof, and an application thereof in MS sealants. The acrylate-modified MS resin described in the present invention has the following structural formula:. The preparation method of the acrylate-modified MS resin comprises the following steps: (1) mixing diisocyanate and acrylate for reaction to obtain a prepolymer; (2) mixing polyether polyol, isocyanate silane, prepolymer, and catalyst for reaction to obtain an acrylate-modified MS resin. The prepared acrylate-modified MS resin is used to prepare MS sealants. The preparation method of the acrylate-modified MS resin provided by the present invention has a simple process, mild reaction conditions, and is convenient for production and conversion. The prepared acrylate-modified MS resin is used in MS sealants to improve the substrate adhesion, weather resistance, and mechanical properties of the MS sealants.

Description

Technical Field

[0001] The invention belongs to the technical field of sealants, and in particular relates to an acrylate-modified MS resin and a preparation method thereof and application of the resin in MS sealants. Background Art

[0002] MS sealant, also known as silane-modified polyether sealant, is a sealant made of MS polymer as the base polymer, combined with fillers, plasticizers and other functional additives. The main chain is polyether, and the end siloxane group is used as the end cap. It has excellent properties such as aging resistance, medium resistance, low foaming at high temperature, no VOC and no irritating odor. MS polymer is a cross-linked polymer based on silane-terminated polyether. Silane-modified polyether sealant has the advantages of silicone sealant and polyurethane sealant, but avoids their disadvantages, such as high staining and low paintability of silicone sealant, and toxic isocyanate and high volatile organic matter of polyurethane sealant. Therefore, silane-modified polyether sealant has broad application prospects in the construction field.

[0003] Although MS sealant has been greatly improved in strength, weather resistance, sprayability and environmental protection, due to structural limitations, its adhesion to metal and plastic materials is poor, resulting in poor bonding effect. Improving the bonding performance of MS sealant and enhancing its adhesion to metal, plastic and other materials needs to be solved urgently. In addition, the selling price of silane end-capping agents is generally high, resulting in a high cost of MS sealant. In order to improve the bonding performance of MS sealant, acrylate-modified polyurethane is often used to improve the bonding performance of sealant. Patent CN114806480A improves the bonding performance of sealant by blending silicone-modified polyurethane resin and acrylic resin with its additives. This preparation method is prone to the risk of phase separation, the product storage is unstable, and the preparation process is relatively complicated; Patent CN117924584A combines polyurethane prepolymer and acrylic resin by solvent copolymerization to obtain acrylic resin modified polyurethane. Although this method is simple and easy to control, toxic solvents are used in the operation process, which seriously pollutes the environment and endangers human health. It does not conform to the development concept of green chemistry, and the solvent needs to be recovered and difficult to reuse, and the production cost is high. Introducing acrylate structure into MS sealant through a simple and feasible method and preparing cost-effective MS sealant with both acrylate and silane termination has become a difficult problem in the industry. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a method for preparing an acrylate-modified MS resin. The process is simple, the reaction conditions are mild, and the production conversion is convenient. The prepared acrylate-modified MS resin is used in MS sealant to improve the substrate adhesion, weather resistance and mechanical properties of the MS sealant.

[0005] The acrylate-modified MS resin of the present invention has the following structural formula:

[0006] ,

[0007] Among them, R is or or -C6H 12 ; R1 is CH2=CHCOOC2H4-, CH2=C(CH3)COOC2H4-, CH2=CHCOOC3H6- or CH2=C(CH3)COOC3H6-; R2 is -C3H6Si(OCH3)3 or -C3H6Si(OCH2CH3)3.

[0008] The preparation method of the acrylate-modified MS resin comprises the following steps: (1) mixing diisocyanate and acrylate to react to obtain a prepolymer; (2) mixing polyether polyol, isocyanate silane, prepolymer and catalyst to react to obtain acrylate-modified MS resin. The catalyst is preferably dibutyltin dilaurate. The reaction temperature of step (1) is 50-60°C, the reaction environment is a nitrogen-protected sealed container, and the number average molecular weight of the obtained prepolymer is 290-394. The reaction temperature of step (2) is 80-90°C, the reaction environment is a nitrogen-protected sealed container, until the viscosity of the material no longer changes, and the acrylate-modified MS resin is obtained.

[0009] The diisocyanate is one of toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI).

[0010] The acrylic acid ester is one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

[0011] The molar ratio of diisocyanate to acrylate is 1-1.05:1.

[0012] The functionality of the polyether polyol is 3, and the number average molecular weight is 12000-20000 g / mol, preferably INOVOL C3180, INOVOL C3120, and INOVOL C3200.

[0013] The isocyanate silane is one of 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane.

[0014] The molar ratio of the polyether polyol to the isocyanate silane is 1:2-2.1; the molar ratio of the polyether polyol to the prepolymer is 1:1-1.05.

[0015] The prepared acrylate-modified MS resin is used to prepare MS sealant, and the MS sealant comprises the following components in parts by weight: 30-40 parts of acrylate-modified MS resin;

[0016] 20-30 parts of plasticizer;

[0017] 40-60 parts of filler;

[0018] 0.5-1 part of UV absorber;

[0019] 0.5-1 part of dewatering agent;

[0020] 1 to 3 parts of adhesion promoter;

[0021] 0.2 to 2 parts of catalyst.

[0022] The dewatering agent is one or both of vinyl trimethoxy silane and vinyl dimethoxy methyl silane.

[0023] The plasticizer is one or both of diisodecyl phthalate and diisononyl phthalate, preferably diisononyl phthalate.

[0024] The filler is one or more of heavy calcium carbonate, light calcium carbonate, nanometer active calcium carbonate and kaolin, preferably one or two of heavy calcium carbonate, nanometer active calcium carbonate and light calcium carbonate.

[0025] The ultraviolet absorber is one or more of benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers; benzotriazole ultraviolet absorbers include UV-326, UV-327, UV-329, etc., and benzophenone ultraviolet absorbers include UV-9, UV-531, UV-B, etc. The ultraviolet absorber is preferably one or both of UV-326 and UV-327.

[0026] The adhesion promoter is one or more of aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropyltrimethoxy, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

[0027] The catalyst is an organic tin catalyst, selected from one or more of dibutyltin dilaurate, monobutyltin triisooctoate, and stannous octoate, preferably one or two of dibutyltin dilaurate and monobutyltin triisooctoate.

[0028] Specifically, the preparation method of the MS sealant is as follows: the prepared acrylate modified MS resin, plasticizer, filler, and ultraviolet absorber are added one by one into a double planetary vacuum power mixer, the stirring and dispersion switches are started, the temperature is increased by high-speed rotation, and vacuum dehydration is performed. When the moisture content of the material is qualified, the machine is stopped, and after the material is naturally cooled, nitrogen is filled to protect and a dehydrating agent, an adhesion promoter, and a catalyst are added step by step, and then the material is stirred under vacuum conditions until the material is evenly mixed, and finally the sealant material is put into an aluminum film plastic bag under nitrogen protection for storage for standby use.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The acrylate-modified MS resin of the present invention adopts a trifunctional ultra-high molecular weight polyether polyol to prepare an acrylate-modified MS resin having both an acrylate structure and a siloxane structure. The high-functionality polyether effectively improves the mechanical strength of the product, and the high molecular weight of the polyether enhances the elastic modulus and elongation of the bonding layer; the introduction of the acrylate structure gives the resin good fluidity, deformation, weather resistance and adhesion to the substrate; the siloxane structure ensures that the resin forms a stable three-dimensional network structure of Si-O-Si bonds during the curing process, giving the material excellent weather resistance, water resistance, aging resistance and durability.

[0031] (2) The one-component MS sealant prepared by the acrylate-modified MS resin prepared by the method of the present invention has excellent bonding properties, mechanical properties and weather resistance, and can be widely used in the fields of prefabricated building components, doors and windows, and automobiles.

[0032] (3) The method for preparing the acrylate-modified MS resin of the present invention has a simple process, low cost, and convenient production and conversion. The prepared target product is used as the base glue of MS sealant and has the dual characteristics of acrylic resin and MS resin, which is convenient for the formulation design and production of downstream MS sealants and better meets market demand. DETAILED DESCRIPTION

[0033] The present invention will be further described below in conjunction with specific embodiments.

[0034] The raw materials used in the examples, unless otherwise specified, are all commercially available conventional raw materials; the process methods used in the examples, unless otherwise specified, are all conventional methods in the art. The weight parts described below are all based on the same unit of mass.

[0035] Some of the raw materials used in the examples and comparative examples are described as follows:

[0036] S303H silane-modified polyether resin, KANEKA Co., Ltd.

[0037] INOVOL C3180, Shandong Yinuowei New Materials Co., Ltd. (functionality 3, number average molecular weight 18000);

[0038] INOVOL C3120, Shandong Yinuowei New Materials Co., Ltd. (functionality 3, number average molecular weight 12000);

[0039] INOVOL C3200, Shandong INOVOL New Materials Co., Ltd. (functionality 3, number average molecular weight 20000).

[0040] Example 1

[0041] (1) Preparation of acrylate-modified MS resin: 30 g of toluene diisocyanate and 20 g of hydroxyethyl acrylate were added to a reaction vessel protected by nitrogen, and the reaction temperature was 50°C. After the reaction was completed, a prepolymer (number average molecular weight of 290) was obtained. 3.625 g of the prepolymer was added with 150 g of INOVOL C3120, 5.13 g of 3-isocyanate propyltrimethoxysilane and 0.02 g of dibutyltin dilaurate, and the temperature was raised to 80°C for reaction until the viscosity of the material no longer changed, thereby obtaining an acrylate-modified MS resin.

[0042] (2) Preparation of MS sealant: 30 parts of acrylate-modified MS resin from step (1), 20 parts of diisononyl phthalate, 50 parts of heavy calcium carbonate, and 0.5 parts of UV-326 were added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches were turned on and the temperature was raised to 110°C at high speed, and vacuum dehydration was performed. The machine was stopped when the moisture content of the material was qualified, and after the material was naturally cooled, 0.5 parts of vinyl trimethoxy silane, 3 parts of N-β-(aminoethyl)-γ-aminopropyl trimethoxy silane, and 0.2 parts of dibutyl tin dilaurate were added step by step under nitrogen protection, and then the materials were stirred under vacuum until the materials were evenly mixed. Finally, the obtained sealant material was put into an aluminum film plastic bag under nitrogen protection and stored for use.

[0043] Example 2

[0044] (1) Preparation of acrylate-modified MS resin: 50 g of 4,4'-diphenylmethane diisocyanate and 26 g of hydroxypropyl acrylate were added to a nitrogen-protected reaction vessel at a reaction temperature of 55°C. The prepolymer (number average molecular weight of 380) was obtained after the reaction was completed. 3.17 g of the prepolymer was added with 150 g of INOVOL C3180, 4.12 g of 3-isocyanate propyl triethoxysilane and 0.02 g of dibutyltin dilaurate, and the temperature was raised to 85°C for reaction until the viscosity of the material no longer changed, thereby obtaining the acrylate-modified MS resin.

[0045] (2) Preparation of MS sealant: 30 parts of acrylate-modified MS resin from step (1), 25 parts of diisononyl phthalate, 20 parts of heavy calcium carbonate, 40 parts of light calcium carbonate, and 1 part of UV-326 were added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches were turned on and the temperature was raised to 110°C at high speed, and vacuum dehydration was performed. The machine was stopped when the moisture content of the material was qualified, and after the material was naturally cooled, 0.5 parts of vinyl trimethoxysilane, 2.5 parts of N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, and 1 part of monobutyl tin triisooctanoate were added step by step under nitrogen protection, and then the materials were stirred under vacuum until the materials were evenly mixed. Finally, the obtained sealant material was put into an aluminum film plastic bag under nitrogen protection and stored for use.

[0046] Example 3

[0047] (1) Preparation of acrylate-modified MS resin: 50 g of 4,4'-diphenylmethane diisocyanate and 30.24 g of hydroxypropyl methacrylate were added to a nitrogen-protected reaction vessel at a reaction temperature of 50°C. The prepolymer (number average molecular weight of 394) was obtained after the reaction was completed. 3.45 g of the prepolymer was added with 150 g of INOVOL C3180, 3.59 g of 3-isocyanate propyl trimethoxysilane and 0.02 g of dibutyltin dilaurate, and the temperature was raised to 90°C for reaction until the viscosity of the material no longer changed, thereby obtaining the acrylate-modified MS resin.

[0048] (2) Preparation of MS sealant: 40 parts of acrylate-modified MS resin from step (1), 20 parts of diisodecyl phthalate, 20 parts of heavy calcium carbonate, 30 parts of nano-activated calcium carbonate, and 0.5 parts of UV-327 are added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches are turned on and the temperature is raised to 110°C at high speed, and then vacuumed and dehydrated. The machine is stopped when the moisture content of the material is qualified. After the material is naturally cooled, 0.5 parts of vinyl dimethoxymethyl silane, 2 parts of N-aminoethyl-3-aminopropylmethyl dimethoxysilane and 0.5 parts of dibutyltin dilaurate are added step by step under nitrogen protection, and then the material is stirred under vacuum until the material is evenly mixed. Finally, the obtained sealant material is put into an aluminum film plastic bag under nitrogen protection and stored for use.

[0049] Example 4

[0050] (1) Preparation of acrylate-modified MS resin: 50 g of hexamethylene diisocyanate and 40.625 g of hydroxyethyl methacrylate were added to a nitrogen-protected reaction vessel at 60°C. The reaction was completed to obtain a prepolymer (number average molecular weight of 298). 2.3 g of the prepolymer was added with 150 g of INOVOL C3200, 3.7 g of 3-isocyanate propyl triethoxysilane and 0.02 g of dibutyltin dilaurate. The temperature was raised to 90°C for reaction until the viscosity of the material no longer changed, thereby obtaining an acrylate-modified MS resin.

[0051] (2) Preparation of MS sealant: 35 parts of acrylate-modified MS resin from step (1), 30 parts of diisononyl phthalate, 10 parts of heavy calcium carbonate, 30 parts of light calcium carbonate, and 0.5 parts of UV-327 were added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches were turned on and the temperature was raised to 110°C at high speed, and vacuum dehydration was performed. The machine was stopped when the moisture content of the material was qualified, and after the material was naturally cooled, 1 part of vinyl dimethoxymethyl silane, 1 part of N-aminoethyl-3-aminopropyl trimethoxy and 2 parts of stannous octoate were added step by step under nitrogen protection, and then the materials were stirred under vacuum until they were evenly mixed. Finally, the obtained sealant material was put into an aluminum film plastic bag under nitrogen protection and stored for later use.

[0052] Comparative Example 1

[0053] 30 parts of S303H silane-modified polyether resin, 20 parts of diisononyl phthalate, 50 parts of heavy calcium carbonate, and 0.5 parts of UV-326 are added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches are turned on and the temperature is raised to 110°C at high speed, and vacuum dehydration is performed. When the moisture content of the material is qualified, the machine is stopped, and after the material is naturally cooled, 0.5 parts of vinyl trimethoxy silane, 3 parts of -N-β-(aminoethyl)-γ-aminopropyl trimethoxy silane and 0.2 parts of dibutyl tin dilaurate are added step by step under nitrogen protection, and then the materials are stirred under vacuum conditions until the materials are evenly mixed. Finally, the obtained sealant material is put into an aluminum film plastic bag under nitrogen protection for storage for standby use.

[0054] Comparative Example 2

[0055] (1) Synthesis of resin: 150 g of C3180, 5.38-isocyanatepropyltrimethoxysilane and 0.02 g of dibutyltin dilaurate were heated to 85°C for reaction until the viscosity of the material no longer changed, thereby obtaining a silane-modified polyether resin.

[0056] (2) Preparation of MS sealant: 30 parts of silane-modified polyether resin from step (1), 25 parts of diisononyl phthalate, 20 parts of heavy calcium carbonate, 40 parts of light calcium carbonate, and 1 part of UV-326 were added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches were turned on and the temperature was raised to 110°C at high speed, and vacuum dehydration was performed. The machine was stopped when the moisture content of the material was qualified, and after the material was naturally cooled, 0.5 parts of vinyl trimethoxysilane, 2.5 parts of N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane and 1 part of monobutyl tin triisooctanoate were added step by step under nitrogen protection, and then the materials were stirred under vacuum until the materials were evenly mixed. Finally, the obtained sealant material was put into an aluminum film plastic bag under nitrogen protection and stored for use.

[0057] Comparative Example 3

[0058] (1) Synthesis of resin: 150 g of C3200, 5.56 g of 3-isocyanatepropyltriethoxysilane and 0.02 g of dibutyltin dilaurate were heated to 80°C for reaction until the viscosity of the material no longer changed, thereby obtaining a silane-modified polyether resin.

[0059] (2) Preparation of MS sealant: 35 parts of silane-modified polyether resin from step (1), 30 parts of diisononyl phthalate, 10 parts of heavy calcium carbonate, 30 parts of light calcium carbonate, and 0.5 parts of UV-327 were added one by one into a double planetary vacuum power mixer, and the stirring and dispersion switches were turned on and the temperature was raised to 110°C at high speed, and then vacuumed and dehydrated. The machine was stopped when the moisture content of the material was qualified, and after the material was naturally cooled, 1 part of vinyl dimethoxymethyl silane, 1 part of N-aminoethyl-3-aminopropyl trimethoxy and 2 parts of stannous octoate were added step by step under nitrogen protection, and then the materials were stirred under vacuum until they were evenly mixed. Finally, the obtained sealant material was put into an aluminum film plastic bag under nitrogen protection and stored for later use.

[0060] The MS sealants prepared in the above Examples 1-4 and Comparative Examples 1-3 were subjected to performance tests, and the test method was as follows:

[0061] (1) Mechanical properties test of MS sealant: refer to GB / T528-2009;

[0062] (2) MS sealant tensile shear strength test: refer to GB / T7124-2008;

[0063] (3) MS sealant bonding performance test: refer to GB / T13477.18-2002.

[0064] The test results are shown in Table 1.

[0065] Table 1 Analysis of performance indicators of MS sealant

[0066]

[0067] As can be seen from Table 1 above, the present invention significantly improves the adhesion of the MS sealant by adding an acrylate structure, and the double bonds and ester groups in the acrylate greatly enhance the adhesion of the colloid itself to the substrate. At the same time, due to the addition of high-functionality polyether polyols, the mechanical properties of the MS sealant are greatly improved.

Claims

1. An acrylate-modified MS resin, characterized in that: It has the following structural formula: ， Among them, R is , or -(CH2)6-; R1 is CH2=CHCOOC2H4-, CH2=C(CH3)COOC2H4-, CH2=CHCOOC3H6- or CH2=C(CH3)COOC3H6-; R2 is -C3H6Si(OCH3)3 or -C3H6Si(OCH2CH3)3; In the above structural formula, " "Polyether polyol" " residue, the functionality of the polyether polyol is 3, and the number average molecular weight is 12000-20000 g / mol.

2. A method for preparing the acrylate-modified MS resin according to claim 1, characterized in that: The method comprises the following steps: (1) mixing diisocyanate and acrylate to react to obtain a prepolymer; (2) mixing polyether polyol, isocyanate silane, prepolymer and catalyst to react to obtain an acrylate-modified MS resin; The diisocyanate is one of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate; The acrylic acid ester is one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; The molar ratio of diisocyanate to acrylate is 1-1.05:1; The isocyanate silane is one of 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane; The molar ratio of the polyether polyol to the isocyanate silane is 1:2-2.1; the molar ratio of the polyether polyol to the prepolymer is 1:1-1.

05.

3. Use of the acrylate-modified MS resin according to claim 1 in MS sealant, characterized in that: The acrylate-modified MS resin is used to prepare the MS sealant, and the MS sealant comprises the following components in parts by weight: 30 to 40 parts of the acrylate-modified MS resin; 20-30 parts of plasticizer; 40-60 parts of filler; 0.5-1 part of UV absorber; 0.5-1 part of dewatering agent; 1 to 3 parts of adhesion promoter; 0.2 to 2 parts of catalyst.

4. The use of the acrylate modified MS resin in MS sealant according to claim 3, characterized in that: The dewatering agent is one or both of vinyl trimethoxy silane and vinyl dimethoxy methyl silane.

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