CN117363296A - High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof - Google Patents

High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof Download PDF

Info

Publication number
CN117363296A
CN117363296A CN202311321482.6A CN202311321482A CN117363296A CN 117363296 A CN117363296 A CN 117363296A CN 202311321482 A CN202311321482 A CN 202311321482A CN 117363296 A CN117363296 A CN 117363296A
Authority
CN
China
Prior art keywords
parts
component
silane
base polymer
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202311321482.6A
Other languages
Chinese (zh)
Other versions
CN117363296B (en
Inventor
刁发进
梁卓恩
黎耀钟
翟晓旭
曹阳杰
章涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Gao Shi Gao Ke Industrial Co ltd
Original Assignee
Guangdong Gao Shi Gao Ke Industrial Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Gao Shi Gao Ke Industrial Co ltd filed Critical Guangdong Gao Shi Gao Ke Industrial Co ltd
Priority to CN202311321482.6A priority Critical patent/CN117363296B/en
Publication of CN117363296A publication Critical patent/CN117363296A/en
Application granted granted Critical
Publication of CN117363296B publication Critical patent/CN117363296B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a high-strength equal-proportion double-component silane modified adhesive and a preparation method thereof, belonging to the technical field of adhesives. The gelatin adhesive is prepared from the following raw materials in parts by weight: 15 to 30 parts of end silane polyether base polymer (1), 15 to 30 parts of end silane polyether base polymer (2), 40 to 70 parts of nano filler, 1.6 to 4 parts of silane coupling agent, 0.1 to 0.3 part of composite vulcanization catalyst and 1 to 3 parts of hydroxyl scavenger. The component B comprises the following raw materials in parts by weight: 20-50 parts of novel active plasticizer, 40-70 parts of filler, 10-20 parts of organosilicon modified epoxy resin and 0.05-0.2 part of curing agent. And the strength and fatigue resistance of the adhesive are improved by adding the organosilicon modified epoxy resin. The novel reactive plasticizer and the base polymer undergo a crosslinking reaction, and cannot exude to the surface of a substrate to cause pollution.

Description

High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of adhesives, and relates to a high-strength equal-proportion double-component silane modified adhesive and a preparation method thereof.
Background
The adhesive is a chemical adhesive, and the two substrates are bonded together through a chemical reaction mechanism. Along with the development of industrial manufacturing production to high efficiency, energy saving, light weight and low cost, the application of the adhesive in industry is more and more important, and replaces the welding, riveting and other processes used in the prior assembly process. The adhesive plays an important role in sealing leakage prevention, improving the strength-to-mass ratio of components, reducing the mass and the like, and has obvious effects on improving the overall performance of the assembly, simplifying the process, improving the production efficiency, reducing the cost and the like.
The silane modified adhesive is an elastomer taking terminal silane polyether or terminal silane polyurethane as a base polymer, matched with filler and auxiliary agent, and capable of being contacted with moisture in air in a room temperature environment to be vulcanized and crosslinked to form the Si-O-Si-based skeleton. And the base polymer maintains the factors similar to polyurethane main chain polyether chain segments on the main chain structure and similar to the polydimethylsiloxane structure of the silicone adhesive base polymer on the end group structure, so that the silane modified polyether base polymer has the excellent performances of polyurethane and silicone adhesive, and the vulcanization by-product is methanol/ethanol, so that the adhesive is environment-friendly to human bodies and environment. The Si-O-Si bond formed after vulcanization provides excellent properties in terms of water resistance, weather resistance, durability, aging resistance and the like for the system.
The reaction mechanism of the silane modified adhesive is that under the condition of moisture (water vapor), terminal silane groups are hydrolyzed to form-OH groups, the-OH groups are condensed with the-OH groups to form an elastomer taking Si-O-Si bonds as a framework, so that the single-component silane modified adhesive has certain limitation in the aspect of curing speed. The silane modified adhesive in the two-component form is far superior to the adhesive in the one-component form in the curing speed performance, but most manufacturers generally have the problems that in order to meet the extrusion service performance, the adhesive strength is low, the thixotropic property is poor and the bonding strength requirement is not met due to low filler addition amount in a system or the extrusion performance is poor due to too high filler addition amount when the conventional powder materials such as nano calcium carbonate, kaolin and the like are used as reinforcing fillers.
Disclosure of Invention
The invention relates to a high-strength equal-proportion double-component silane modified adhesive and a preparation method thereof, belonging to the technical field of adhesives. The gelatin adhesive is prepared from the following raw materials in parts by weight: 15 to 30 parts of end silane polyether base polymer (1), 15 to 30 parts of end silane polyether base polymer (2), 40 to 70 parts of nano filler, 1.6 to 4 parts of silane coupling agent, 0.1 to 0.3 part of composite vulcanization catalyst and 1 to 3 parts of hydroxyl scavenger. The component B comprises the following raw materials in parts by weight: 20-50 parts of novel active plasticizer, 40-70 parts of filler, 10-20 parts of organosilicon modified epoxy resin and 0.05-0.2 part of curing agent. And the strength and fatigue resistance of the adhesive are improved by adding the organosilicon modified epoxy resin. The novel reactive plasticizer and the base polymer undergo a crosslinking reaction, and cannot exude to the surface of a substrate to cause pollution.
The aim of the invention can be achieved by the following technical scheme:
the high-strength equal-proportion type double-component silane modified adhesive is prepared from the following raw materials in parts by weight: 15 to 30 parts of end silane polyether base polymer (1), 15 to 30 parts of end silane polyether base polymer (2), 40 to 70 parts of nano filler, 1.6 to 4 parts of silane coupling agent, 0.1 to 0.3 part of composite vulcanization catalyst and 1 to 3 parts of hydroxyl scavenger. The component B comprises the following raw materials in parts by weight: 20-50 parts of novel active plasticizer, 40-70 parts of filler, 10-20 parts of organosilicon modified epoxy resin and 0.05-0.2 part of curing agent.
Further, the structural formulas of the silyl terminated polyether base polymer (1) and the silyl terminated polyether base polymer (2) are as follows,
silyl terminated polyether base polymer (1):
silyl terminated polyether base polymer (2):
further, the nanofiller is modified nano calcium carbonate, and the silane coupling agent is (CH) 3 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 Or (C) 2 H 5 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 The hydroxyl scavenger is vinyl trimethoxy silane.
Further, the composite vulcanization catalyst consists of an epoxy accelerator DMP-30 and diacetyl dibutyl tin in a mass ratio of 1:1, the curing agent is sodium glycerophosphate, and the structural formula of the novel active plasticizer is as follows:
further, the preparation method of the organosilicon modified epoxy resin comprises the following steps:
a1: mixing epoxy resin and stannous octoate, heating to obtain a substance A, and preserving heat for 15min;
a2: and adding polysiloxane for multiple times, stirring and heating, stopping heating after the reaction, and cooling to obtain the organosilicon modified epoxy resin.
Further, stannous octoate in the step A1 accounts for 0.15% of the mass of the epoxy resin, and the temperature is raised to 70 ℃.
Further, the multiple times in the step A2 are 3-4 times, the polysiloxane accounts for 6% of the mass of the epoxy resin, and the temperature rise is to 85 ℃.
Further, the reaction time in the step A2 is 2h, and the cooling is to be 30 ℃.
The preparation method of the high-strength equal-proportion double-component silane modified adhesive comprises the following steps:
s1: mixing the nanofiller and the silane-terminated polyether base polymer (2) under vacuum condition, heating for dehydration, cooling, adding the silane-terminated polyether base polymer (1), stirring in vacuum, adding a hydroxyl scavenger, a silane coupling agent and a composite vulcanization catalyst, and stirring to obtain a component A;
s2: mixing and stirring the novel active plasticizer and the filler, then cooling, adding the organosilicon modified epoxy resin and the curing agent, and stirring to obtain a component B;
s3: and (3) mixing the component A obtained in the step (S1) and the component B obtained in the step (S2) according to the mass ratio of 1:1 to form the double-component silane modified adhesive.
Further, in the step S1, the mixing time is 2-3 hours, heating means heating to 100-110 ℃, dehydration means water content is reduced to 300-500 ppm, cooling means reducing to 25-45 ℃, vacuum stirring time is 15-25 min, stirring time is 30-45 min, mixing stirring time is 2 hours in the step S2, cooling means reducing to 30-50 ℃, and stirring time is 30-45 min.
The invention has the beneficial effects that:
(1) The double-component adhesive solves the problem that the single-component adhesive is affected by humidity in the environment and has low curing speed in a low-temperature and low-humidity environment.
(2) And the strength and fatigue resistance of the adhesive are improved by adding the organosilicon modified epoxy resin, and meanwhile, the adhesive has good extrudability and is convenient to use.
(3) The novel active plasticizer and the base polymer undergo a crosslinking reaction, and the adhesive cannot ooze to the surface of a substrate to cause pollution in the use process.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
The component A of the double-component silane modified adhesive comprises the following raw materials in parts by weight: silane-terminated polyether base polymer (1) 15 parts, silane-terminated polyether base polymer (2) 15 parts, nanofiller 40 parts, silane coupling agent 1.6 parts, composite vulcanization catalyst 0.1 parts, and hydroxyl scavenger 1 part. The component B comprises the following raw materials in parts by weight: 20 parts of novel active plasticizer, 40 parts of calcium carbonate, 10 parts of organosilicon modified epoxy resin and 0.05 part of curing agent.
The structural formulas of the end-silane polyether base polymer (1) and the end-silane polyether base polymer (2) are as follows,
silyl terminated polyether base polymer (1):
silyl terminated polyether base polymer (2):
purchase source of the silyl terminated polyether base polymer (1): the manufacturer is KANEKA, product model S303H, the purchase source of the silyl terminated polyether base polymer (2): the manufacturer is WACKER and the product model is E-15.
The nano filler is modified nano calcium carbonate, and the silane coupling agent is (CH) 3 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 The hydroxyl scavenger is vinyl trimethoxy silane.
Purchase source of the modified nano calcium carbonate: the manufacturer is the Japan white stone industry, model number is the Brilliant TOD.
The silane coupling agent is prepared by reacting amino alkyl alkoxy silane with acryloxy alkoxy silane, and the reaction formula is as follows:
the composite vulcanization catalyst consists of an epoxy accelerator DMP-30 and diacetyl dibutyl tin in a mass ratio of 1:1, wherein the curing agent is sodium glycerophosphate, and the structural formula of the novel active plasticizer is as follows:
purchase source of the reactive plasticizer: the manufacturer is WACKER and model number XM25.
The preparation method of the organosilicon modified epoxy resin comprises the following steps:
a1: mixing epoxy resin and stannous octoate, heating to obtain a substance A, and preserving heat for 15min;
a2: and adding polysiloxane for multiple times, stirring and heating, stopping heating after the reaction, and cooling to obtain the organosilicon modified epoxy resin.
The stannous octoate in the step A1 accounts for 0.15% of the mass of the epoxy resin, and the temperature is raised to 70 ℃.
The multiple times in the step A2 are 3 times, the polysiloxane accounts for 6% of the mass of the epoxy resin, and the temperature rise is to 85 ℃.
The reaction time in the step A2 is 2h, and the cooling is to be 30 ℃.
The preparation method of the high-strength equal-proportion double-component silane modified adhesive comprises the following steps:
s1: mixing 40 parts by weight of nanofiller and 15 parts by weight of silane-terminated polyether base polymer (2) under vacuum condition, heating for dehydration, then cooling, adding 15 parts by weight of silane-terminated polyether base polymer (1), stirring in vacuum, then adding 1 part by weight of hydroxyl scavenger, 1.6 parts by weight of silane coupling agent and 0.1 part by weight of composite vulcanization catalyst, and stirring to obtain a component A;
s2: mixing and stirring 20 parts by weight of novel active plasticizer and 40 parts by weight of filler, then cooling and adding 10 parts by weight of organosilicon modified epoxy resin and 0.05 part by weight of curing agent, and stirring to obtain a component B;
s3: and (3) mixing the component A obtained in the step (S1) and the component B obtained in the step (S2) according to the mass ratio of 1:1 to form the double-component silane modified adhesive.
The mixing time in the step S1 is 2 hours, heating is to heat to 100 ℃, dehydration is to reduce the water content to 300ppm, cooling is to reduce the water content to 25 ℃, the vacuum stirring time is 15 minutes, the stirring time is 30 minutes, the mixing stirring time in the step S2 is 2 hours, cooling is to reduce the water content to 30 ℃, and the stirring time is 30 minutes.
Example 2
The component A of the double-component silane modified adhesive comprises the following raw materials in parts by weight: silane-terminated polyether base polymer (1) 22 parts, silane-terminated polyether base polymer (2) 22 parts, nanofiller 55 parts, silane coupling agent 3 parts, composite vulcanization catalyst 0.2 parts, and hydroxyl scavenger 2 parts. The component B comprises the following raw materials in parts by weight: 35 parts of novel active plasticizer, 55 parts of calcium carbonate, 15 parts of organosilicon modified epoxy resin and 0.1 part of curing agent.
The structural formulas of the end-silane polyether base polymer (1) and the end-silane polyether base polymer (2) are as follows,
silyl terminated polyether base polymer (1):
silyl terminated polyether base polymer (2):
purchase source of the silyl terminated polyether base polymer (1): the manufacturer is KANEKA, product model S303H, the purchase source of the silyl terminated polyether base polymer (2): the manufacturer is WACKER and the product model is E-15.
The nano filler is modified nano calcium carbonate, and the silane coupling agent is (CH) 3 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 The hydroxyl scavenger is vinyl trimethoxy silane.
Purchase source of the modified nano calcium carbonate: the manufacturer is the Japan white stone industry, model number is the Brilliant TOD.
The silane coupling agent is prepared by reacting amino alkyl alkoxy silane with acryloxy alkoxy silane, and the reaction formula is as follows:
the composite vulcanization catalyst consists of an epoxy accelerator DMP-30 and diacetyl dibutyl tin in a mass ratio of 1:1, wherein the curing agent is sodium glycerophosphate, and the structural formula of the novel active plasticizer is as follows:
purchase source of the reactive plasticizer: the manufacturer is WACKER and model number XM25.
The preparation method of the organosilicon modified epoxy resin comprises the following steps:
a1: mixing epoxy resin and stannous octoate, heating to obtain a substance A, and preserving heat for 15min;
a2: and adding polysiloxane for multiple times, stirring and heating, stopping heating after the reaction, and cooling to obtain the organosilicon modified epoxy resin.
The stannous octoate in the step A1 accounts for 0.15% of the mass of the epoxy resin, and the temperature is raised to 70 ℃.
The multiple times in the step A2 are 3 times, the polysiloxane accounts for 6% of the mass of the epoxy resin, and the temperature rise is to 85 ℃.
The reaction time in the step A2 is 2h, and the cooling is to be 30 ℃.
The preparation method of the high-strength equal-proportion double-component silane modified adhesive comprises the following steps:
s1: mixing 55 parts by weight of nanofiller and 22 parts by weight of silane-terminated polyether base polymer (2) under vacuum condition, heating for dehydration, then cooling, adding 22 parts by weight of silane-terminated polyether base polymer (1), stirring in vacuum, then adding 2 parts by weight of hydroxyl scavenger, 3 parts by weight of silane coupling agent and 0.2 part by weight of composite vulcanization catalyst, and stirring to obtain a component A;
s2: mixing 35 parts by weight of novel active plasticizer and 55 parts by weight of filler, stirring, then cooling, adding 15 parts by weight of organosilicon modified epoxy resin and 0.1 part by weight of curing agent, and stirring to obtain a component B;
s3: and (3) mixing the component A obtained in the step (S1) and the component B obtained in the step (S2) according to the mass ratio of 1:1 to form the double-component silane modified adhesive.
The mixing time in the step S1 is 2.5h, heating is heating to 105 ℃, dehydration is that water content is reduced to 400ppm, cooling is that water content is reduced to 35 ℃, the vacuum stirring time is 20min, the stirring time is 38min, the mixing stirring time in the step S2 is 2h, cooling is that water content is reduced to 40 ℃, and the stirring time is 38min.
Example 3
The component A of the double-component silane modified adhesive comprises the following raw materials in parts by weight: silane-terminated polyether base polymer (1) 30 parts, silane-terminated polyether base polymer (2) 30 parts, nanofiller 70 parts, silane coupling agent 4 parts, composite vulcanization catalyst 0.3 parts, and hydroxyl scavenger 3 parts. The component B comprises the following raw materials in parts by weight: 50 parts of novel active plasticizer, 70 parts of calcium carbonate, 20 parts of organosilicon modified epoxy resin and 0.2 part of curing agent.
The structural formulas of the end-silane polyether base polymer (1) and the end-silane polyether base polymer (2) are as follows,
silyl terminated polyether base polymer (1):
silyl terminated polyether base polymer (2):
purchase source of the silyl terminated polyether base polymer (1): the manufacturer is KANEKA, product model S303H, the purchase source of the silyl terminated polyether base polymer (2): the manufacturer is WACKER and the product model is E-15.
The nano filler is modified nano calcium carbonate, and the silane coupling agent is (CH) 3 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 The hydroxyl scavenger is vinyl trimethoxy silane.
Purchase source of the modified nano calcium carbonate: the manufacturer is the Japan white stone industry, model number is the Brilliant TOD.
The silane coupling agent is prepared by reacting amino alkyl alkoxy silane with acryloxy alkoxy silane, and the reaction formula is as follows:
the composite vulcanization catalyst consists of an epoxy accelerator DMP-30 and diacetyl dibutyl tin in a mass ratio of 1:1, wherein the curing agent is sodium glycerophosphate, and the structural formula of the novel active plasticizer is as follows:
purchase source of the reactive plasticizer: the manufacturer is WACKER and model number XM25.
The preparation method of the organosilicon modified epoxy resin comprises the following steps:
a1: mixing epoxy resin and stannous octoate, heating to obtain a substance A, and preserving heat for 15min;
a2: and adding polysiloxane for multiple times, stirring and heating, stopping heating after the reaction, and cooling to obtain the organosilicon modified epoxy resin.
The stannous octoate in the step A1 accounts for 0.15% of the mass of the epoxy resin, and the temperature is raised to 70 ℃.
The multiple times in the step A2 are 3 times, the polysiloxane accounts for 6% of the mass of the epoxy resin, and the temperature rise is to 85 ℃.
The reaction time in the step A2 is 2h, and the cooling is to be 30 ℃.
The preparation method of the high-strength equal-proportion double-component silane modified adhesive comprises the following steps:
s1:70 parts by weight of nanofiller and 30 parts by weight of silane-terminated polyether base polymer (2) are mixed under vacuum condition, heated for dehydration, then 30 parts by weight of silane-terminated polyether base polymer (1) is added for vacuum stirring, then 3 parts by weight of hydroxyl scavenger, 4 parts by weight of silane coupling agent and 0.3 part by weight of composite vulcanization catalyst are added, and stirring is carried out to obtain a component A;
s2:50 parts by weight of novel active plasticizer and 70 parts by weight of filler are mixed and stirred, then 20 parts by weight of organosilicon modified epoxy resin and 0.2 part by weight of curing agent are added by cooling, and the mixture is stirred to obtain a component B;
s3: and (3) mixing the component A obtained in the step (S1) and the component B obtained in the step (S2) according to the mass ratio of 1:1 to form the double-component silane modified adhesive.
The mixing time in the step S1 is 3 hours, the heating is heating to 110 ℃, the dehydration is that the moisture is reduced to 500ppm, the cooling is that the moisture is reduced to 55 ℃, the vacuum stirring time is 25 minutes, the stirring time is 45 minutes, the mixing stirring time in the step S2 is 2 hours, the cooling is that the moisture is reduced to 50 ℃, and the stirring time is 45 minutes.
Comparative example 1
Based on the example 2, the A component in the raw material component of the high-strength equal-proportion double-component silane modified adhesive and the A component in the preparation process are removed, and the main agent in the 3MDP 605NS double-component adhesive with equal mass ratio is used for substitution, and other conditions are the same as those of the example 2.
The purchase sources of the 3MDP 605NS are: dongguan city Yihui adhesive Co.
Comparative example 2
Based on the example 2, the B component in the raw material component of the high-strength equal-proportion double-component silane modified adhesive and the B component in the preparation process are removed, and the curing agent in the 3MDP 605NS double-component adhesive with equal mass ratio is used for substitution, and other conditions are the same as those of the example 2.
The purchase sources of the 3MDP 605NS are: dongguan city Yihui adhesive Co.
Comparative example 3
On the basis of example 2, the organosilicon modified epoxy resin in the raw material components of the high-strength equal-proportion double-component silane modified adhesive and the organosilicon modified epoxy resin in the preparation process are removed, and other conditions are the same as in example 2.
Comparative example 4
Based on the example 2, the novel active plasticizer in the raw material component of the high-strength equal-proportion double-component silane modified adhesive and the novel active plasticizer in the preparation process are removed, and the dibutyl phthalate plasticizer with equal weight parts is used for substitution, and other conditions are consistent with the example 2.
1. Gel time test
The high strength equal proportion type double component silane modified adhesives prepared in examples 1-3 and comparative examples 1-2 were divided into 5 groups, and the gel time of each group was measured according to patent CN 112375209A, the test condition temperature was-5-0 ℃, and the relative humidity was 80%. The blank test was conducted at a temperature of 25 to 30℃and a relative humidity of 50 to 60%. The test results are shown in Table 1.
TABLE 1 gel time test of adhesives
As can be seen directly from Table 1, the gels of examples 1-3 used less than comparative examples 1-2. The two-component adhesives prepared in examples 1 to 3 are superior to the two-component adhesives prepared in comparative examples 1 to 2, are less affected by humidity in the environment, and have a smaller difference between the curing speed in a low-temperature and low-humidity environment and the curing speed in a normal-temperature condition.
2. Tensile shear fatigue Performance test
The high strength, equal proportion, two-component silane modified adhesives prepared in example 2 and comparative example 3 were each prepared in 16 samples, with 4 samples tested at one level. It was tested for tensile shear fatigue performance according to GB/T27595-2011. Table 2 shows the data obtained from the tensile shear fatigue test.
TABLE 2 data results of tensile shear fatigue Performance test
Note that: pi is the proportion of the level that destroyed the sample.
From the data in Table 2, it is found that the tensile shear fatigue properties of example 2 are superior to those of comparative example 3. And the tensile shear fatigue performance of the adhesive is improved by adding the organosilicon modified epoxy resin.
3. Penetration test
The high strength, equal proportion, two-component silane modified adhesives prepared in examples 1-3 and comparative example 4 were used as test samples. The wood plate, the natural marble and the electronic main board device are used as the base materials, and the base materials are bonded at normal temperature to observe the exudation of the plasticizer. Each sample was tested 3 times and recorded and the experimental results are shown in table 3.
TABLE 3 penetration test results
Note that: plasticizer exudation contamination is indicated by "+" and no leakage is indicated by "-".
As is clear from table 3, examples 1 to 3 did not show the bleeding of the plasticizer, whereas comparative example 4 showed the bleeding of the plasticizer and was relatively large in all of the wood block, the natural marble and the electronic motherboard device. The novel active plasticizer and the base polymer undergo a crosslinking reaction, and the adhesive cannot ooze to the surface of a substrate to cause pollution in the use process.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.

Claims (10)

1. The high-strength equal-proportion double-component silane modified adhesive is characterized by being prepared from an A component and a B component in equal mass ratio, wherein the A component comprises the following raw materials in parts by weight: 15 to 30 parts of end silane polyether base polymer (1), 15 to 30 parts of end silane polyether base polymer (2), 40 to 70 parts of nano filler, 1.6 to 4 parts of silane coupling agent, 0.1 to 0.3 part of composite vulcanization catalyst and 1 to 3 parts of hydroxyl scavenger. The component B comprises the following raw materials in parts by weight: 20-50 parts of novel active plasticizer, 40-70 parts of filler, 10-20 parts of organosilicon modified epoxy resin and 0.05-0.2 part of curing agent.
2. The high-strength equal-proportion type two-component silane modified adhesive according to claim 1, wherein the structural formulas of the end-silyl polyether base polymer (1) and the end-silyl polyether base polymer (2) are as follows,
silyl terminated polyether base polymer (1):
silyl terminated polyether base polymer (2):
3. the high-strength equal-proportion type two-component silane modified adhesive according to claim 1, wherein the nanofiller is modified nano calcium carbonate, and the silane coupling agent is (CH 3 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 Or (b)
(C 2 H 5 O) 3 SiC 3 H 6 NHCH 2 CH 2 COOC 3 H 6 Si(OCH 3 ) 3 The hydroxyl scavenger is vinyl trimethoxy silane.
4. The high-strength equal-proportion type two-component silane modified adhesive is characterized in that the composite vulcanization catalyst consists of an epoxy accelerator DMP-30 and diacetyl dibutyl tin in a mass ratio of 1:1, the curing agent is sodium glycerophosphate, and the structural formula of the novel active plasticizer is as follows:
5. the high-strength equal-proportion type two-component silane modified adhesive according to claim 1, wherein the preparation method of the organosilicon modified epoxy resin comprises the following steps:
a1: mixing epoxy resin and stannous octoate, heating to obtain a substance A, and preserving heat for 15min;
a2: and adding polysiloxane for multiple times, stirring and heating, stopping heating after the reaction, and cooling to obtain the organosilicon modified epoxy resin.
6. The high-strength equal-proportion type two-component silane modified adhesive according to claim 5, wherein stannous octoate in the step A1 accounts for 0.15% of the mass of the epoxy resin, and the temperature is raised to 70 ℃.
7. The high-strength equal-proportion type two-component silane modified adhesive according to claim 5, wherein the multiple times in the step A2 are 3-4 times, the polysiloxane accounts for 6% of the mass of the epoxy resin, and the temperature rise is to 85 ℃.
8. The high-strength equal-proportion type two-component silane modified adhesive according to claim 5, wherein the reaction time in the step A2 is 2h, and the cooling is to 30 ℃.
9. A method for preparing the high-strength equal-proportion type double-component silane modified adhesive according to any one of claims 1 to 8, which is characterized in that the method for preparing the high-strength equal-proportion type double-component silane modified adhesive comprises the following steps:
s1: mixing the nanofiller and the silane-terminated polyether base polymer (2) under vacuum condition, heating for dehydration, cooling, adding the silane-terminated polyether base polymer (1), stirring in vacuum, adding a hydroxyl scavenger, a silane coupling agent and a composite vulcanization catalyst, and stirring to obtain a component A;
s2: mixing and stirring the novel active plasticizer and the filler, then cooling, adding the organosilicon modified epoxy resin and the curing agent, and stirring to obtain a component B;
s3: and (3) mixing the component A obtained in the step (S1) and the component B obtained in the step (S2) according to the mass ratio of 1:1 to form the double-component silane modified adhesive.
10. The method for preparing a high-strength equal-proportion type double-component silane modified adhesive according to claim 9, wherein the mixing time in the step S1 is 2-3 h, heating is to 100-110 ℃, dehydration is to 300-500 ppm of water, cooling is to 25-45 ℃, vacuum stirring is performed for 15-25 min, stirring is performed for 30-45 min, mixing and stirring are performed for 2h in the step S2, cooling is to 30-50 ℃, and stirring is performed for 30-45 min.
CN202311321482.6A 2023-10-13 2023-10-13 High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof Active CN117363296B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311321482.6A CN117363296B (en) 2023-10-13 2023-10-13 High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311321482.6A CN117363296B (en) 2023-10-13 2023-10-13 High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof

Publications (2)

Publication Number Publication Date
CN117363296A true CN117363296A (en) 2024-01-09
CN117363296B CN117363296B (en) 2024-06-25

Family

ID=89399751

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311321482.6A Active CN117363296B (en) 2023-10-13 2023-10-13 High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117363296B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118064094A (en) * 2024-04-24 2024-05-24 有行鲨鱼（上海）科技股份有限公司 Single-component MS epoxy structural adhesive for new energy automobile and preparation method thereof

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819549A (en) * 1972-02-04 1974-06-25 Shinetsu Chemical Co Room temperature vulcanizing organosilicone compositions
US20030229192A1 (en) * 2002-05-31 2003-12-11 Frisch Kurt C. Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings
CN102206478A (en) * 2011-04-22 2011-10-05 东莞市普赛达密封粘胶有限公司 Environment-friendly silyl-terminated polyether sealant and preparation method thereof
CN104293273A (en) * 2014-10-17 2015-01-21 苏州之诺新材料科技有限公司 Epoxy resin modified dual-component silicyl-terminated polyether adhesive
CN105295811A (en) * 2015-11-30 2016-02-03 广州市高士实业有限公司 High-shear and single-component silane-modified polyether sealant and preparation method thereof
CN106833478A (en) * 2016-12-30 2017-06-13 北京华腾新材料股份有限公司 A kind of high-performance refractory type double-component silane modified polyether seal glue and preparation method
CN109897589A (en) * 2019-01-23 2019-06-18 雨中情防水技术集团有限责任公司 A kind of high-elastic sealant of environment-friendly type and preparation method thereof
CN110157376A (en) * 2019-06-06 2019-08-23 广州市白云化工实业有限公司 Transparent two-component silane modified polyether seal glue and preparation method thereof
CN110699028A (en) * 2019-10-25 2020-01-17 杭州之江新材料有限公司 Two-component silyl-terminated polyether modified sealant and preparation method thereof
CN110734730A (en) * 2018-07-20 2020-01-31 东莞市博君来胶粘材料科技有限公司 silane modified polyether two-component sealant and preparation method thereof
CN111393966A (en) * 2020-04-28 2020-07-10 杭州之江新材料有限公司 Solvent-free silane-terminated modified polyether three-proofing paint and preparation method thereof
CN111574950A (en) * 2020-06-08 2020-08-25 厦门韦尔通科技有限公司 Ultra-soft silane modified polyether adhesive with buffering performance and preparation method thereof
CN111704864A (en) * 2019-07-19 2020-09-25 广州市高士实业有限公司 Silane modified polyether sealant and preparation method and application thereof
CN112080246A (en) * 2020-08-31 2020-12-15 仲恺农业工程学院 Organic silicon pouring sealant and preparation method thereof
CN112980374A (en) * 2021-03-24 2021-06-18 杭州之江新材料有限公司 Two-component silane modified sealant and preparation method thereof
CN113025254A (en) * 2021-02-04 2021-06-25 东莞市德聚胶接技术有限公司 Non-tin catalytic silane modified polyether sealant and preparation method thereof
CN113150737A (en) * 2021-02-07 2021-07-23 广东莱雅新化工科技有限公司 Two-component organic silicon pouring sealant and preparation method thereof
CN113512393A (en) * 2021-07-29 2021-10-19 佛山市科顺建筑材料有限公司 Soaking-resistant flame-retardant single-component silane modified polyether sealant and preparation method thereof
CN115558452A (en) * 2022-04-18 2023-01-03 浙江凌志新材料有限公司 Bi-component structural adhesive for bonding power battery and preparation method thereof
CN116162432A (en) * 2022-12-08 2023-05-26 北京天山新材料技术有限公司 Two-component modified silane adhesive and application thereof
CN116355573A (en) * 2023-02-27 2023-06-30 东莞市德聚胶接技术有限公司 Silane modified polyether sealant with multiple bonding functions and preparation method thereof
US20230272253A1 (en) * 2020-07-22 2023-08-31 Bostik Sa Adhesive composition for making waterproof breathable articles

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819549A (en) * 1972-02-04 1974-06-25 Shinetsu Chemical Co Room temperature vulcanizing organosilicone compositions
US20030229192A1 (en) * 2002-05-31 2003-12-11 Frisch Kurt C. Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings
CN102206478A (en) * 2011-04-22 2011-10-05 东莞市普赛达密封粘胶有限公司 Environment-friendly silyl-terminated polyether sealant and preparation method thereof
CN104293273A (en) * 2014-10-17 2015-01-21 苏州之诺新材料科技有限公司 Epoxy resin modified dual-component silicyl-terminated polyether adhesive
CN105295811A (en) * 2015-11-30 2016-02-03 广州市高士实业有限公司 High-shear and single-component silane-modified polyether sealant and preparation method thereof
CN106833478A (en) * 2016-12-30 2017-06-13 北京华腾新材料股份有限公司 A kind of high-performance refractory type double-component silane modified polyether seal glue and preparation method
CN110734730A (en) * 2018-07-20 2020-01-31 东莞市博君来胶粘材料科技有限公司 silane modified polyether two-component sealant and preparation method thereof
CN109897589A (en) * 2019-01-23 2019-06-18 雨中情防水技术集团有限责任公司 A kind of high-elastic sealant of environment-friendly type and preparation method thereof
CN110157376A (en) * 2019-06-06 2019-08-23 广州市白云化工实业有限公司 Transparent two-component silane modified polyether seal glue and preparation method thereof
CN111704864A (en) * 2019-07-19 2020-09-25 广州市高士实业有限公司 Silane modified polyether sealant and preparation method and application thereof
CN110699028A (en) * 2019-10-25 2020-01-17 杭州之江新材料有限公司 Two-component silyl-terminated polyether modified sealant and preparation method thereof
CN111393966A (en) * 2020-04-28 2020-07-10 杭州之江新材料有限公司 Solvent-free silane-terminated modified polyether three-proofing paint and preparation method thereof
CN111574950A (en) * 2020-06-08 2020-08-25 厦门韦尔通科技有限公司 Ultra-soft silane modified polyether adhesive with buffering performance and preparation method thereof
US20230272253A1 (en) * 2020-07-22 2023-08-31 Bostik Sa Adhesive composition for making waterproof breathable articles
CN112080246A (en) * 2020-08-31 2020-12-15 仲恺农业工程学院 Organic silicon pouring sealant and preparation method thereof
CN113025254A (en) * 2021-02-04 2021-06-25 东莞市德聚胶接技术有限公司 Non-tin catalytic silane modified polyether sealant and preparation method thereof
CN113150737A (en) * 2021-02-07 2021-07-23 广东莱雅新化工科技有限公司 Two-component organic silicon pouring sealant and preparation method thereof
CN112980374A (en) * 2021-03-24 2021-06-18 杭州之江新材料有限公司 Two-component silane modified sealant and preparation method thereof
CN113512393A (en) * 2021-07-29 2021-10-19 佛山市科顺建筑材料有限公司 Soaking-resistant flame-retardant single-component silane modified polyether sealant and preparation method thereof
CN115558452A (en) * 2022-04-18 2023-01-03 浙江凌志新材料有限公司 Bi-component structural adhesive for bonding power battery and preparation method thereof
CN116162432A (en) * 2022-12-08 2023-05-26 北京天山新材料技术有限公司 Two-component modified silane adhesive and application thereof
CN116355573A (en) * 2023-02-27 2023-06-30 东莞市德聚胶接技术有限公司 Silane modified polyether sealant with multiple bonding functions and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118064094A (en) * 2024-04-24 2024-05-24 有行鲨鱼（上海）科技股份有限公司 Single-component MS epoxy structural adhesive for new energy automobile and preparation method thereof

Also Published As

Publication number Publication date
CN117363296B (en) 2024-06-25

Similar Documents

Publication Publication Date Title
CN108546543B (en) Organosilicon sealant and preparation method and application thereof
CN108504318B (en) High-transparency and high-strength silane modified polyether elastic sealant and preparation method thereof
CN109054715B (en) Modified silane sealant for LED backlight source and preparation method thereof
CN113493614B (en) High-efficiency bonding bi-component room temperature vulcanized silicone rubber and preparation method thereof
CN108484803B (en) Silane-terminated polymer and moisture-cured adhesive composition prepared from same
CN107523259B (en) Preparation of alpha-570 coupling agent modified organosilicon sealant
CN109810670B (en) Bi-component fireproof silicone sealant and preparation method thereof
CN114702676B (en) Single-component low-viscosity quick-solid dealcoholization RTV silicone rubber and preparation method thereof
CN111040715A (en) Single-component reaction type polyurethane hot melt adhesive and preparation method thereof
CN111732924A (en) Single-component silane modified polyether sealant and preparation method thereof
CN110577747A (en) room temperature vulcanized fluorosilicone rubber and preparation method thereof
CN111718486A (en) Thixotropic agent and two-component silicone sealant containing same
CN109181623B (en) Silicone sealant for fast curing photovoltaic module and preparation method thereof
CN111303828B (en) Single-component alcohol-type sealant and preparation method thereof
CN111073577B (en) Environment-friendly MS sealant and preparation method thereof
WO2022193662A1 (en) One-component silane-modified polyether sealant, preparation method therefor and application thereof
CN114874744A (en) Mildew-proof beauty glue for interior decoration and preparation method thereof
CN113956840A (en) Dealcoholized room temperature vulcanized silicone rubber sealant and preparation method thereof
CN112210341B (en) Double-vulcanization system building sealant and preparation method thereof
CN117363296B (en) High-strength equal-proportion type double-component silane modified adhesive and preparation method thereof
CN113308186A (en) Flame-retardant silane modified waterproof coating and preparation method thereof
CN110257002B (en) Two-component silicone sealant for projection lamp
CN108484916B (en) Modified vinyl silicone oil, preparation method thereof, printing silica gel base adhesive containing modified vinyl silicone oil, and printing silica gel
CN111394035A (en) High-strength transparent nail-free glue and preparation method thereof
CN110776867A (en) Antibacterial silane polyether adhesive and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant