CN114958257A - High-performance sealant and preparation method thereof - Google Patents

High-performance sealant and preparation method thereof Download PDF

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Publication number
CN114958257A
CN114958257A CN202210403183.6A CN202210403183A CN114958257A CN 114958257 A CN114958257 A CN 114958257A CN 202210403183 A CN202210403183 A CN 202210403183A CN 114958257 A CN114958257 A CN 114958257A
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parts
modified polymer
silane modified
stirring kettle
stirring
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Inventor
林春霞
王建斌
陈田安
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Yantai Darbond Technology Co Ltd
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Yantai Darbond Technology Co Ltd
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Priority to CN202210403183.6A priority Critical patent/CN114958257A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00Adhesives 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
    • C09J151/08Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention relates to a high-performance sealant which is prepared from the following raw materials in parts by weight: 35-55 parts of silane modified polymer-polyacrylate copolymer, 5-15 parts of plasticizer, 25-45 parts of reinforcing filler, 1-10 parts of pigment, 1-2 parts of ultraviolet absorber, 1-2 parts of light stabilizer, 1-3 parts of tackifier and 0.5-2 parts of catalyst. The invention also discloses a preparation method of the adhesive. The adhesive prepared by the invention has good adhesion and weather resistance, and overcomes the defects of the existing silane modified polymer sealant.

Description

High-performance sealant and preparation method thereof
Technical Field
The invention relates to the field of adhesives, in particular to a high-performance sealant and a preparation method thereof.
Background
Since the 20 th century and the 70 th century, several types of silane modified polymer sealants are developed successively in Japan, Europe and America and other countries, active siloxane is used for sealing polyether or polyurethane polymer to prepare the silane modified polymer sealant, the silane modified polymer sealant can absorb moisture at room temperature, is crosslinked and cured to form a three-dimensional reticular structure, does not generate toxic and harmful gas molecules in the reaction process, and accords with the trend of green environmental protection. Because the adhesive has the advantages and the advantages of silicone sealant and polyurethane windshield glass adhesive, the adhesive has the advantages of excellent weather resistance, durability, high deformation displacement resistance, good cohesiveness, paintability, environmental friendliness, low staining property, low viscosity, excellent construction property and the like, and is widely applied, such as: the building field, the industrial field, the electronic and electric appliance field and the like, particularly, the development in China has been extremely rapid in the last decade.
Silane-modified polymer sealants, while having a number of advantages, have been shown to be unsatisfactory in some applications. Such as: acrylic acid structural adhesive is mainly used in the front of the elevator industry, has the characteristics of high curing speed and high strength, but has large smell, irritation to human bodies and environmental friendliness. In recent years, many elevator manufacturers aim to silane modified polymer sealant to replace acrylic structural adhesive, but the strength of the sealant is lower when the sealant is used at elevator reinforcing ribs. In addition, the sealing and bonding of the front windshield glass of the automobile always uses polyurethane windshield glass glue, which has high strength but can achieve good bonding effect only by using a primer; meanwhile, the viscosity is high, the sizing process is poor, especially in winter, the viscosity is very high, the construction can be normally carried out only after the glue is heated in advance, the construction efficiency is influenced, and the production cost is increased.
The invention relates to a high-performance sealant which is developed mainly aiming at glue points for sealing and bonding elevator reinforcing ribs and automobile windshield glass, and the like, and is required to have good construction property and adhesion property in the using process so as to keep good sealing property.
Disclosure of Invention
The invention provides a high-performance sealant which has good adhesion and weather resistance on elevator and automobile windshield glass and solves some defects in the existing silane modified polymer sealant.
The technical scheme for solving the problems is as follows: a high-performance sealant comprises the following raw materials in parts by weight: 35-55 parts of silane modified polymer-polyacrylate copolymer, 5-15 parts of plasticizer, 25-45 parts of reinforcing filler, 1-10 parts of pigment, 1-2 parts of ultraviolet absorber, 1-2 parts of light stabilizer, 1-3 parts of tackifier and 0.5-2 parts of catalyst.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the silane modified polymer-polyacrylate copolymer is subjected to copolymerization modification by using acrylate on the basis of the silane modified polymer, so that the aim of improving the strength of the copolymer is fulfilled.
The structural formula of the silane modified polymer is as follows:
Figure BDA0003601142510000021
structural formula I
Figure BDA0003601142510000022
Structural formula II
In the two structural formulas:
Figure BDA0003601142510000023
(n=50~150)
R 1 one of methyl, ethyl, methoxy and ethoxy,
R 2 one of methoxy group and ethoxy group,
R 3 =-CH 2 -、-(CH 2 ) 3 -。
the specific preparation method of the silane modified polymer-polyacrylate copolymer comprises the following steps:
adding 100 parts of butyl acrylate, 100 parts of 2-methyl methacrylate, 0.2 part of azodiisobutyronitrile and 0.003 part of dodecyl mercaptan into a stirring kettle, stirring for 20 minutes, adding 500 parts of silane modified polymer with the structural formula I into the stirring kettle, heating to 70 ℃, reacting for 3 hours at the temperature, then heating to 120 ℃, and continuing to react for 2 hours to obtain the silane modified polymer-polyacrylate copolymer I.
Adding 100 parts of butyl acrylate, 100 parts of 2-methyl methacrylate, 0.2 part of azodiisobutyronitrile and 0.003 part of dodecyl mercaptan into a stirring kettle, stirring for 20 minutes, adding 500 parts of silane modified polymer with the structural formula II into the stirring kettle, heating to 70 ℃, reacting for 3 hours at the temperature, then heating to 120 ℃, and continuing to react for 2 hours to obtain the silane modified polymer-polyacrylate copolymer.
Further, the plasticizer is one or a mixture of several of diisononyl phthalate, dioctyl phthalate and diisodecyl phthalate.
Further, the reinforcing filler is one or a mixture of several of nano active calcium carbonate, carbon black and fumed silica.
Further, the pigment is one of titanium dioxide and carbon black.
Further, the light stabilizer is bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate.
Further, the ultraviolet light absorber is 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazole.
Further, the tackifier is one or a mixture of more of N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
Further, the catalyst is one or a mixture of more of U-220H, U-303 and stannous octoate formed by chemical reaction in the east China.
The preparation method of the high-strength sealant comprises the following steps: sequentially adding 35-55 parts of silane modified polymer-polyacrylate copolymer, 5-15 parts of plasticizer, 25-45 parts of reinforcing filler, 1-10 parts of pigment, 1-2 parts of ultraviolet absorber and 1-2 parts of light stabilizer into a double-planet stirring kettle, stirring and dispersing at 100-110 ℃, carrying out vacuum dehydration for 2 hours, cooling to below 50 ℃ under the condition that the vacuum degree is not less than-0.098 MPa, adding 1-3 parts of tackifier into the stirring kettle, mixing for 10 minutes under the protection of nitrogen, adding 0.5-2 parts of catalyst into the stirring kettle, mixing for 10 minutes under the vacuum state, wherein the vacuum degree is not less than-0.098 MPa, and sealing and packaging with nitrogen.
The invention has the beneficial effects that: the high-strength sealant provided by the invention has high adhesive force of the cured adhesive layer to a base material, completely meets the strength requirements of different application points on the adhesive, and also has good constructability and environmental friendliness.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Adding 35 parts of silane modified polymer-polyacrylate copolymer, 5 parts of diisononyl phthalate, 25 parts of nano active calcium carbonate, 1 part of titanium dioxide, 1 part of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 1 part of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazole into a double-planet stirring kettle in sequence, stirring and dispersing at 100-110 ℃ and carrying out vacuum dehydration for 2 hours under the condition that the vacuum degree is not less than-0.098 MPa, cooling to below 50 ℃, adding 0.5 part of N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane and 0.5 part of gamma-methacryloxypropyltrimethoxysilane into the double-planet stirring kettle, mixing for 10 minutes under the protection of nitrogen, finally adding 0.5 part of U-220H into the stirring kettle, mixing for 10 minutes under the vacuum state, vacuum degree not less than-0.098 MPa, N 2 Sealing and packaging.
Example 2
Adding 55 parts of silane modified polymer-polyacrylate copolymer, 15 parts of diisodecyl phthalate, 45 parts of nano active calcium carbonate, 10 parts of titanium dioxide, 2 parts of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazole into a double-planet stirring kettle in sequence, stirring and dispersing at 100-110 ℃ and carrying out vacuum dehydration for 2 hours, wherein the vacuum degree is not less than-0.098 MPa, cooling to below 50 ℃, adding 2 parts of aminopropyltriethoxysilane and 1 part of gamma-methacryloxypropyltrimethoxysilane into the double-planet stirring kettle, mixing for 10 minutes under the protection of nitrogen, finally adding 2 parts of U-303 into the stirring kettle, mixing for 10 minutes under the vacuum state, vacuum degree not less than-0.098 MPa, N 2 Sealing and packaging.
Example 3
45 parts of silane modified polymer-polyacrylate copolymer, 12 parts of dioctyl phthalate, 30 parts of nano active calcium carbonate, 5 parts of carbon black, 1.5 parts of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 1.5 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazoleAdding the mixture into a double-planetary stirring kettle, stirring and dispersing the mixture at the temperature of between 100 and 110 ℃, dehydrating the mixture in vacuum for 2 hours with the vacuum degree of not less than-0.098 MPa, cooling the mixture to the temperature of below 50 ℃, adding 1 part of aminopropyl trimethoxysilane and 1 part of gamma-methacryloxypropyl trimethoxysilane into the double-planetary stirring kettle, mixing the mixture for 10 minutes under the protection of nitrogen, finally adding 1 part of stannous octoate into the stirring kettle, mixing the mixture for 10 minutes under the vacuum state with the vacuum degree of not less than-0.098 MPa, and performing N-side dehydration on the mixture for 2 hours 2 Sealing and packaging.
Example 4
Adding 25 parts of silane modified polymer-polyacrylate copolymer I, 20 parts of silane modified polymer-polyacrylate copolymer II, 15 parts of diisononyl phthalate, 35 parts of nano active calcium carbonate, 5 parts of fumed silica, 8 parts of carbon black, 2 parts of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazole into a double-planetary stirring kettle in sequence, stirring and dispersing at 100-110 ℃ and carrying out vacuum dehydration for 2 hours, wherein the vacuum degree is not less than-0.098 MPa, cooling to below 50 ℃, adding 1.5 parts of N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane and 1 part of gamma-methacryloxypropyltrimethoxysilane into the double-planetary stirring kettle, mixing for 10 minutes under the protection of nitrogen, finally, adding 1.5 parts of U-220H into the stirring kettle, and mixing for 10 minutes in a vacuum state, wherein the vacuum degree is not less than-0.098 MPa, and N is 2 Sealing and packaging.
The examples 1 to 4 are compared with the general silane modified polymer sealant, the polyurethane windshield glass adhesive and the acrylic acid structural adhesive for performance tests, the mechanical property data are obtained by testing after curing for 7 days under the conditions of 23 +/-2 ℃ and 50 +/-5% of relative humidity, and the specific test results are shown in the following table 1.
Test examples
The performance of a high strength, high adhesion silane modified polymer-polyacrylate type binder of the present invention was tested by the following test.
Test example 1
The tensile shear strength was tested according to GB/T7124-2008.
Test example 2
Adhesion: GB/T13477.18-2002.
Test example 3
Tensile strength was tested according to GB/T528-.
Test example 4
The extrusion rate was in accordance with GB/T13477.4-2002.
The test results are given in the following table:
Figure BDA0003601142510000061
Figure BDA0003601142510000071
the test results in the table show that the silane modified polymer-polyacrylate type adhesive with high strength and high adhesive force prepared by the invention has good adhesive property to various substrates, and the strength is obviously superior to that of the general silane modified polymer sealant; compared with acrylic acid structural adhesive, the strength is slightly lower, but the use requirement is completely met, and no pungent smell exists; compared with the polyurethane windshield glass glue, the high-strength polyurethane windshield glass glue has the advantages of high strength, good application property, good weather resistance and low smell, and can well replace the polyurethane windshield glass glue.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A high-performance sealant comprises the following raw materials in parts by weight: 35-55 parts of silane modified polymer-polyacrylate copolymer, 5-15 parts of plasticizer, 25-45 parts of reinforcing filler, 1-10 parts of pigment, 1-2 parts of ultraviolet absorber, 1-2 parts of light stabilizer, 1-3 parts of tackifier and 0.5-2 parts of catalyst.
2. The high performance sealant of claim 1, wherein the silane modified polymer-polyacrylate copolymer is a silane modified polymer copolymerized with acrylate, and the silane modified polymer has the following two structural formulas:
Figure FDA0003601142500000011
in the two structural formulas:
Figure FDA0003601142500000012
(n=50~150)
R 1 one of methyl, ethyl, methoxy and ethoxy,
R 2 one of methoxy group and ethoxy group,
R 3 =-CH 2 -、-(CH 2 ) 3 -。
3. the high-performance sealant according to claim 1 or 2, wherein the silane-modified polymer-polyacrylate copolymer is prepared by the following specific method:
adding 100 parts of butyl acrylate, 100 parts of 2-methyl methacrylate, 0.2 part of azodiisobutyronitrile and 0.003 part of dodecyl mercaptan into a stirring kettle, stirring for 20 minutes, adding 500 parts of silane modified polymer with the structural formula I into the stirring kettle, heating to 70 ℃, reacting for 3 hours at the temperature, then heating to 120 ℃, and continuing to react for 2 hours to obtain a silane modified polymer-polyacrylate copolymer I;
adding 100 parts of butyl acrylate, 100 parts of 2-methyl methacrylate, 0.2 part of azodiisobutyronitrile and 0.003 part of dodecyl mercaptan into a stirring kettle, stirring for 20 minutes, adding 500 parts of silane modified polymer with the structural formula II into the stirring kettle, heating to 70 ℃, reacting for 3 hours at the temperature, then heating to 120 ℃, and continuing to react for 2 hours to obtain the silane modified polymer-polyacrylate copolymer.
4. The high performance sealant according to claim 1, wherein the plasticizer is one or more of diisononyl phthalate, dioctyl phthalate and diisodecyl phthalate.
5. The high-performance sealant according to claim 1, wherein the reinforcing filler is one or a mixture of several of nano activated calcium carbonate, carbon black and fumed silica; the pigment is one of titanium dioxide and carbon black; the light stabilizer is bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate; the ultraviolet light absorber is 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butyl) -5-chloro-benzotriazole.
6. The high-performance sealant according to claim 1, wherein the tackifier is one or a mixture of N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane and aminopropyltriethoxysilane; the catalyst is one or a mixture of more of U-220H, U-303 and stannous octoate formed by chemical reaction in Nidong.
7. The high performance sealant and the preparation method thereof as claimed in any one of claims 1 to 6, wherein the preparation method comprises: sequentially adding 35-55 parts of silane modified polymer-polyacrylate copolymer, 5-15 parts of plasticizer, 25-45 parts of reinforcing filler, 1-10 parts of pigment, 1-2 parts of ultraviolet absorber and 1-2 parts of light stabilizer into a double-planet stirring kettle, stirring and dispersing at 100-110 ℃, carrying out vacuum dehydration for 2 hours, cooling to below 50 ℃ under the condition that the vacuum degree is not less than-0.098 MPa, adding 1-3 parts of tackifier into the stirring kettle, mixing for 10 minutes under the protection of nitrogen, adding 0.5-2 parts of catalyst into the stirring kettle, mixing for 10 minutes under the vacuum state, wherein the vacuum degree is not less than-0.098 MPa, and sealing and packaging with nitrogen.
CN202210403183.6A 2022-04-18 2022-04-18 High-performance sealant and preparation method thereof Pending CN114958257A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173137A (en) * 2011-12-22 2013-06-26 汉高股份有限公司 Ultraviolet-curable and moisture-curable adhesive composition
CN108192551A (en) * 2017-12-30 2018-06-22 广州市白云化工实业有限公司 Transparent, high adhesiveness silane-modified adhesive and preparation method thereof
CN109679556A (en) * 2018-12-20 2019-04-26 烟台德邦科技有限公司 A kind of preparation method of the silane-modified sealant of environment-friendly type
CN110903800A (en) * 2019-12-12 2020-03-24 湖南柯盛新材料有限公司 Building sealant and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103173137A (en) * 2011-12-22 2013-06-26 汉高股份有限公司 Ultraviolet-curable and moisture-curable adhesive composition
CN108192551A (en) * 2017-12-30 2018-06-22 广州市白云化工实业有限公司 Transparent, high adhesiveness silane-modified adhesive and preparation method thereof
CN109679556A (en) * 2018-12-20 2019-04-26 烟台德邦科技有限公司 A kind of preparation method of the silane-modified sealant of environment-friendly type
CN110903800A (en) * 2019-12-12 2020-03-24 湖南柯盛新材料有限公司 Building sealant and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
兰云军, 中国轻工业出版社 *

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