WO2022193662A1

WO2022193662A1 - One-component silane-modified polyether sealant, preparation method therefor and application thereof

Info

Publication number: WO2022193662A1
Application number: PCT/CN2021/126416
Authority: WO
Inventors: 陈洋庆; 陈建军; 高敏华; 唐华; 黄恒超; 缪明松
Original assignee: 广州市白云化工实业有限公司
Priority date: 2021-03-17
Filing date: 2021-10-26
Publication date: 2022-09-22
Also published as: CN113025253B; CN113025253A

Abstract

Provided in the present invention are a one-component silane-modified polyether sealant, a preparation method therefor and the application thereof. The preparation raw materials for the one-component silane-modified polyether sealant comprise, in parts by weight, the following components: 25-50 parts of a silane-modified polyether resin, 5-30 parts of a reinforced resin, 10-50 parts of a plasticizer, 0.1-3 parts of a rheological agent, 0.5-3 parts of a stabilizer, and 0.5-3 parts of a dehydrator. The one-component silane-modified polyether sealant prepared in the present invention has the characteristics of high transparency and high strength and is suitable for the fields of interior decoration, bonding of automobile windshields, bonding of locomotive structures, etc.

Description

One-component silane-modified polyether sealant and preparation method and application thereof

technical field

The invention belongs to the technical field of sealants, and relates to a one-component silane-modified polyether sealant and a preparation method and application thereof, in particular to a high-transparency and high-strength one-component silane-modified polyether sealant and preparation thereof methods and applications.

Background technique

Silane-modified polyether adhesive, also known as modified silicone adhesive, is a high-performance adhesive prepared from silane-terminated polyether polymer as the base resin. Silane-terminated polyether was first developed by Japan Zhongyuan Chemical in 1979. Its main chain is polyether, and its end groups are hydrolyzable silane end groups, which are similar to silicone glue. The silane-terminated polyether has a macromolecular pure ether chain structure on the main chain. It does not contain urethane bonds and urea bonds with high cohesive energy like the main chain of polyurethane, which not only brings good flexibility to the base resin. It has good flexibility, high elongation and hydrolysis resistance, and significantly reduces the viscosity of silane-terminated polyether, which is beneficial to the silane-modified polyether sealant system that can obtain good process performance without or with less solvent or plasticizer. And maintain the balance of excellent overall performance of the system.

Silane-modified polyether sealants have the advantages of environmental friendliness, paintability, and the versatility of bonding materials, but conventional silane-modified polyether sealants are mostly opaque paste-like compounds with relatively low strength. , which limits its application in applications requiring high bonding strength, high tensile strength and high transparency, such as in the field of high-end residential interior decoration and automotive windshield bonding, it still cannot replace transparent silicone glue and high mechanical strength polyurethane sealant.

At present, in order to improve the mechanical properties of transparent silane-modified polyether sealants on the market, the more commonly used method is to use fumed silica as a reinforcing filler. The use of fumed silica can improve the transparent silane-modified polyether sealant to a certain extent. The mechanical properties of the glue are limited, but the improvement is limited, and the tensile strength (≤4MPa) and bonding strength are still low. Too much silica will harm human health and even cause pneumoconiosis. The two-component transparent sealant needs to be mixed evenly with the matching glue equipment before it can be constructed and used. The operation is complicated and its application is limited.

CN111732924A discloses a one-component silane-modified polyether sealant and a preparation method thereof. The one-component silane-modified polyether sealant includes silane-modified polyether polymer, silane-modified polyether resin, plasticizer, Pigment and filler, dehydrating agent, silane coupling agent, catalyst, light stabilizer, ultraviolet absorber. Due to the introduction of amino groups and epoxy groups in this invention, the hardness, bulk strength and adhesion of the prepared sealant Strength is significantly increased. However, the transparency of the sealant of the invention needs to be further improved.

CN111218248A discloses a transparent one-component silane-modified polyether sealant. The raw materials of the silane-modified polyether sealant include the following components: silane-modified polyether resin, plasticizer, inorganic filler, water removal agents, UV absorbers, light stabilizers, silane coupling agents and catalysts. The silane-modified polyether sealant of the invention has a simple preparation process, and has high transparency and/or good anti-ultraviolet performance. However, the transparency and tensile strength of the sealant of the invention need to be further improved.

CN109337629A discloses a high-modulus transparent silane-modified polyether sealant, which is made from the following raw material components: silane-modified polyether resin, plasticizer, light stabilizer, antioxidant, color paste, white Carbon black, water scavengers, adhesion promoters and catalysts. The high-modulus transparent silane-modified polyether sealant of the invention has the characteristics of good transparency, good weather resistance, high tensile modulus, high bonding strength, paintability, and no free NCO. It has excellent comprehensive performance and can be applied In interior decoration, automobile manufacturing, electronic appliances and glass counters and other fields. However, the tensile strength of the sealant of the invention needs to be further improved, and the preparation raw material of the invention contains white carbon black, which will cause harm to human health.

Therefore, in the art, it is desired to develop a high-transparency, high-strength one-component silane-modified polyether sealant.

SUMMARY OF THE INVENTION

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a one-component silane-modified polyether sealant and its preparation method and application, especially to provide a high-transparency, high-strength one-component silane-modified polyether sealant Sealant and preparation method and application thereof. In the present invention, high transparency refers to the light transmittance of the silane-modified polyether sealant tested in accordance with GB/T2410-2008>85%, and high strength refers to the silane-modified polyether sealant tested in accordance with GB/T528-2009. Tensile strength>5MPa.

For this purpose, the present invention adopts the following technical solutions:

In one aspect, the present invention provides a one-component silane-modified polyether sealant, and the raw materials for preparing the one-component silane-modified polyether sealant, in parts by weight, include the following components:

The reinforcing resin has the following structural features:

Among them, m, n are integers and 1≤m≤50, for example, m is 1, 2, 3, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45 or 50, etc., 1≤n≤ 25, for example, n is 1, 2, 3, 5, 8, 10, 15, 20 or 25, etc. The ratio of m to n is (1~2):1, for example, the ratio of m to n is 1:1, 1.3 : 1, 1.5:1, 1.8:1 or 2:1, etc., R is any one of methyl, ethyl or phenyl or a combination of at least two, such as methyl and Ethyl, methyl and ethyl and phenyl and the like.

The present invention uses α-silane-terminated silane-modified polyether resin as the base resin, adds reinforcing resin, and reasonably adjusts the mass percentage of each component to prepare the single-component silane-modified polyether sealant, which, on the one hand, retains the silane-modified polyether sealant. On the other hand, similar to the silane-modified polyether resin, the reinforcing resin is also end-capped with -Si-OCH ₃ , which can participate in the moisture curing process. Reaction, thereby increasing the crosslinking density of the sealant, thereby improving the mechanical properties of the sealant.

In the present invention, in the preparation raw materials of the one-component silane-modified polyether sealant, the dosage of the silane-modified polyether resin can be 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts, 48 or 50, etc.

In the present invention, in the preparation raw materials of the one-component silane-modified polyether sealant, the dosage of the reinforcing resin can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, etc.

In the present invention, in the preparation raw materials of the one-component silane-modified polyether sealant, the amount of plasticizer can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 or 50, etc.

In the present invention, in the preparation raw materials of the one-component silane-modified polyether sealant, the dosage of the rheological agent can be 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.5 part, 2 part, 2.5 servings or 3 servings etc.

In the present invention, in the preparation raw materials of the one-component silane-modified polyether sealant, the amount of the stabilizer can be 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, etc.

In the present invention, in the raw materials for the preparation of the one-component silane-modified polyether sealant, the amount of the water scavenger can be 0.5, 0.8, 1, 1.5, 2, 2.5 or 3 parts, etc. .

In the present invention, the silane-modified polyether resin is a silane-modified polyether resin end-capped with α-silane, and has the following structural features:

Wherein, Me is methyl.

Preferably, the silane-modified polyether resin includes any one or a combination of at least two of STP-E10 resin, STP-E30 resin or STP-XB502 resin produced by WACKER, Germany. A combination of the at least two kinds, such as STP-E10 resin and STP-E30 resin, STP-E10 resin and STP-E30 resin, and STP-XB502 resin, etc.

In the present invention, the preparation method of the reinforced resin comprises the following steps:

(1) adding epoxy resin to polyetheramine, heating up, and reacting to obtain modified epoxy resin;

(2) heating up, adding trialkoxysilane to the modified epoxy resin in step (1), then adding a catalyst, and performing a vacuum stirring reaction to obtain the reinforced resin.

The reaction mechanism is as follows:

(1) ring-opening reaction between epoxy group and amino group:

(2) The hydroxyl group in the modified epoxy resin reacts with trialkoxysilane:

In the present invention, the reinforced resin is prepared by the reaction of epoxy resin, polyetheramine, alkyl trialkoxy silane or phenyl trialkoxy silane, so that it retains the characteristics of epoxy resin and amino silane at the same time, and has High strength and high adhesion, so the one-component silane-modified polyether sealant with reinforcing resin has good adhesion to various substrates, and does not need to add silane coupling agent to improve adhesion. In addition, the α-silane-terminated silane-modified polyether resin does not need to add an organotin catalyst, and can be cross-linked and cured with moisture in the air under the catalysis of only aminosilane, which reduces the harm of organotin and is not immune to certain These areas limit the influence of organotin, thereby expanding the scope of use.

In the present invention, the polyetheramine is a bifunctional polyetheramine resin whose main chain is a polyether structure and the terminal active functional group is a bifunctional amine group.

Preferably, the molecular weight of the polyetheramine is 100-3000, such as 100, 300, 500, 800, 1000, 1500, 1800, 2000, 2500 or 3000, and the like.

Preferably, the polyetheramine comprises any one or a combination of at least two of Huntsman D230, D400 or D2000. A combination of the at least two, such as D230 and D400, D230 and D2000, and the like.

Preferably, the epoxy resin is a bisphenol A epoxy resin.

Preferably, the molecular weight of the epoxy resin is 600-5000, such as 600, 800, 1000, 2000, 3000, 4000 or 5000, etc.

Preferably, the epoxy resin comprises any one or a combination of at least two of E44, E51 or E35 commercially available in Nanya, Taiwan. A combination of the at least two, such as E44 and E51, E44 and E51, and E35, etc.

Preferably, the trialkoxysilane includes alkyltrialkoxysilane and/or aryltrialkoxysilane, preferably methyltrimethoxysilane, ethyltrimethoxysilane or phenyltrimethoxysilane Any one or a combination of at least two, such as methyltrimethoxysilane and ethyltrimethoxysilane, ethyltrimethoxysilane and phenyltrimethoxysilane, etc., Methyltrimethoxysilane is preferred.

Preferably, the catalyst comprises dibutyltin dilaurate.

In the present invention, epoxy resin is added to polyetheramine in step (1), and the molar ratio of polyetheramine to epoxy resin is 1:(0.5-1.5), for example, 1:0.5, 1:0.8, 1 :1, 1:1.2 or 1:1.5 etc.

Preferably, described in step (2), add trialkoxysilane to the modified epoxy resin of step (1), and the ratio of the number of moles of trialkoxysilane to the number of moles of hydroxyl groups in the modified epoxy resin is 1: (0.1～1), such as 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.8 or 1:1, etc.

Preferably, the added amount of the catalyst is 0.1-1% of the mass of the trialkoxysilane, such as 0.1%, 0.2%, 0.3%, 0.5%, 0.8% or 1%, etc.

In the present invention, the temperature increase in step (1) is to increase the temperature to 50-60°C, for example, 50°C, 52°C, 54°C, 56°C, 58°C, or 60°C.

Preferably, the reaction time of step (1) is 4-8h, such as 4h, 5h, 5.5h, 6h, 7h or 8h, etc.

Preferably, in step (2), the temperature is raised to 80-120°C, such as 80°C, 85°C, 90°C, 95°C, 100°C, 110°C or 120°C, and the like.

Preferably, the time of the vacuum stirring reaction in step (2) is 1-6h, such as 1h, 2h, 3h, 4h, 5h or 6h, etc.

In the present invention, the plasticizer includes any one or a combination of at least two of the polyether polyols PPG1000, PPG2000, PPG3000, PPG4000 or PPG8000. Combinations of the at least two, such as PPG1000 and PPG2000, PPG3000 and PPG4000, and PPG8000, etc.

Preferably, the rheological agent is a liquid thixotropic agent, preferably BYK-410 from BYK.

Preferably, the stabilizer is a liquid stabilizer, preferably BASF B75.

Preferably, the water scavenger is a vinyl functional silane type water scavenger, including any one or at least one of vinyltrimethoxysilane, vinyltriethoxysilane or vinylmethyldimethoxysilane combination of the two. Combinations of the at least two such as vinyltrimethoxysilane and vinyltriethoxysilane, vinyltriethoxysilane and vinylmethyldimethoxysilane, and the like.

On the other hand, the present invention provides the above-mentioned preparation method of one-component silane-modified polyether sealant, and the preparation method comprises the following steps:

Mix the silane-modified polyether resin, rheology agent, stabilizer, part of plasticizer and water scavenger evenly, then add the remaining plasticizer and reinforcing resin, stir under vacuum conditions, and defoaming to obtain the monolayer. Components Silane-modified polyether sealant.

In the present invention, the rotating speed of the mixing is 5-15rpm, such as 5rpm, 8rpm, 10rpm, 13rpm or 15rpm, etc., and the mixing time is 20-60min, such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.

Preferably, the vacuum degree of the vacuum condition is -0.09 to -0.1 MPa, such as -0.09 MPa, -0.092 MPa, -0.093 MPa, -0.095 MPa, -0.098 MPa or -0.1 MPa, and the like.

Preferably, the rotational speed of the stirring is 5-10rpm, 5rpm, 6rpm, 7rpm, 8rpm, 9rpm or 10rpm, etc., and the stirring time is 15-60min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min , 55min or 60min, etc.

In another aspect, the present invention provides the application of the above-mentioned one-component silane-modified polyether sealant in interior decoration, automobile windshield or locomotive structural bonding.

Compared with the prior art, the present invention at least has the following beneficial effects:

(1) The present invention uses silane-modified polyether resin as the base resin, and adds reinforcing resin to prepare a one-component silane-modified polyether sealant, which on the one hand retains the flexibility and durability of silane-modified polyether resin. On the other hand, its mechanical properties (tensile strength: 5.3-8.8MPa, tensile shear strength: 4.1-7.3MPa) are improved;

(2) Compared with the traditional silane-modified polyether sealant, the single-component silane-modified polyether sealant prepared by the present invention retains the properties of epoxy resin and amino silane because the preparation raw materials contain reinforcing resin. It has high strength and high adhesion, so it has good adhesion to various substrates, and does not need to add silane coupling agent to improve adhesion. In addition, because the reinforcing resin in the sealant of the present invention has a structure similar to that of the aminosilane coupling agent, the α-silane-terminated silane-modified polyether resin can be cross-linked with moisture in the air without adding an organotin catalyst. For curing, there is no need to add aminosilane coupling agent and organotin as catalyst, which reduces the harm of organotin, and is not affected by the restriction of organotin in some fields, thus expanding its scope of use;

(3) The one-component silane-modified polyether sealant of the present invention uses a reinforcing resin to improve its mechanical properties, and has better performance than the traditional transparent silane-modified polyether sealant using fumed silica as a reinforcing filler. High transparency (light transmittance: 92-93%) and can prevent human health from inhaling too much silica powder during the production process;

(4) Compared with the two-component polyether sealant, the one-component silane-modified polyether sealant of the present invention has simpler construction and is compared with the conventional opaque paste-like one-component silane-modified polyether sealant. , Because powder with higher water content is not used as reinforcing filler in the formula system, high temperature dehydration is not required during production, the process is simple, easy to operate, and the production cost is low, which is conducive to industrial production and use.

Detailed ways

The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

Example 1

In this embodiment, a one-component silane-modified polyether sealant is provided, and the preparation raw materials of the one-component silane-modified polyether sealant, in parts by weight, include the following components:

The reinforcing resin has the following structural features:

Among them, the ratio of m to n is 1:1, and R is methyl.

The silane-modified polyether resin is a silane-modified polyether resin end-capped with α-silane, and has the following structural features:

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D230 into the reaction kettle, according to the molar ratio of polyetheramine D230 and epoxy resin E44 as 1:1, slowly add epoxy resin E44 under low-speed stirring, heat up to 55°C, and react for 5h to obtain Modified epoxy resin;

(2) slowly heating the reaction kettle to 90°C, according to the ratio of the mole number of methyltrimethoxysilane to the mole number of hydroxyl groups in the modified epoxy resin, 1:0.1, to the modified epoxy resin of step (1) Methyltrimethoxysilane was added, and then a catalyst, dibutyltin dilaurate, was added dropwise, and the reaction was stirred under vacuum for 3 hours to obtain the reinforced resin.

Wherein, the addition amount of catalyst dibutyltin dilaurate is 0.1% of the mass of methyltrimethoxysilane.

The preparation method of one-component silane-modified polyether sealant comprises the following steps:

Mix silane-modified polyether resin STP-E10, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG3000 (10 parts) and water scavenger vinyltrimethoxysilane at a low speed of 10rpm for 40min and mix well , and then adding the remaining plasticizer PPG3000 and reinforcing resin, stirring at a speed of 5 rpm for 30 minutes under -0.09MPa vacuum condition, and defoaming to obtain the single-component silane-modified polyether sealant.

Example 2

The reinforcing resin has the following structural features:

Wherein, the ratio of m to n is 1.1:1, and R is ethyl.

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D400 into the reaction kettle, according to the molar ratio of polyetheramine D400 and epoxy resin E35 of 1:0.8, slowly add epoxy resin E35 under low-speed stirring, heat up to 55 ° C, and react for 4 h to obtain Modified epoxy resin;

(2) slowly heating the reaction kettle to 100°C, according to the ratio of the mole number of ethyltrimethoxysilane to the mole number of hydroxyl groups in the modified epoxy resin, the ratio is 1:1, to the modified epoxy resin of step (1) Ethyltrimethoxysilane was added, and then the catalyst dibutyltin dilaurate was added dropwise, and the reaction was stirred under vacuum for 1 h to obtain the reinforced resin.

Wherein, the addition amount of catalyst dibutyltin dilaurate is 0.5% of the mass of ethyltrimethoxysilane.

Silane-modified polyether resin STP-E30, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG8000 (20 parts) and water scavenger vinyltriethoxysilane were mixed at a low speed of 10rpm for 60min uniformly, then add the remaining plasticizer PPG8000 and reinforcing resin, stir for 60 minutes at a speed of 5 rpm under -0.1MPa vacuum condition, and defoaming to obtain the single-component silane-modified polyether sealant.

Example 3

The reinforcing resin has the following structural features:

Wherein, the ratio of m to n is 1.5:1, and R is phenyl.

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D2000 into the reaction kettle, according to the molar ratio of polyetheramine D2000 and epoxy resin E44 of 1:1.2, slowly add epoxy resin E44 under low-speed stirring, heat up to 50 ° C, and react for 7 hours to obtain Modified epoxy resin;

(2) slowly heating the reaction kettle to 90°C, according to the ratio of the mole number of phenyltrimethoxysilane to the mole number of hydroxyl groups in the modified epoxy resin, 1:0.5, to the modified epoxy resin of step (1) Phenyltrimethoxysilane was added, and then the catalyst dibutyltin dilaurate was added dropwise, and the reaction was stirred under vacuum for 5 hours to obtain the reinforced resin.

Wherein, the addition amount of catalyst dibutyltin dilaurate is 1% of the mass of phenyltrimethoxysilane.

Mix silane-modified polyether resin STP-XB502, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG4000 (30 parts) and water scavenger vinyltrimethoxysilane at a low speed of 10rpm for 20min and mix well , and then adding the remaining plasticizer PPG4000 and reinforcing resin, stirring at 5 rpm for 40 min under vacuum conditions of -0.095 MPa, and defoaming to obtain the single-component silane-modified polyether sealant.

Example 4

The reinforcing resin has the following structural features:

Wherein, the ratio of m to n is 1.8:1, and R is phenyl.

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D2000 into the reaction kettle, according to the molar ratio of polyetheramine D2000 to epoxy resin E44 of 1:1.5, slowly add epoxy resin E44 under low-speed stirring, heat up to 50 ° C, and react for 7 hours to obtain Modified epoxy resin;

Mix silane-modified polyether resin STP-XB502, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG4000 (20 parts) and water scavenger vinyltrimethoxysilane at a low speed of 10rpm for 20min and mix well , and then adding the remaining plasticizer PPG4000 and reinforcing resin, stirring at 5 rpm for 40 min under vacuum conditions of -0.095 MPa, and defoaming to obtain the single-component silane-modified polyether sealant.

Example 5

The reinforcing resin has the following structural features:

Among them, the ratio of m to n is 1.3:1, and R is methyl.

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D400 into the reaction kettle, according to the molar ratio of polyetheramine D400 and epoxy resin E51 of 1:0.5, slowly add epoxy resin E51 under low-speed stirring, heat up to 60 ° C, and react for 8 hours to obtain Modified epoxy resin;

(2) slowly heating the reaction kettle to 80°C, according to the ratio of the number of moles of methyltrimethoxysilane to the number of moles of hydroxyl groups in the modified epoxy resin, 1:0.3, to the modified epoxy resin of step (1) Methyltrimethoxysilane was added, and then a catalyst, dibutyltin dilaurate, was added dropwise, and the reaction was stirred under vacuum for 6 hours to obtain the reinforced resin.

Wherein, the addition amount of catalyst dibutyltin dilaurate is 0.8% of the mass of methyltrimethoxysilane.

Silane-modified polyether resin STP-E10, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG1000 (5 parts) and water scavenger vinylmethyldimethoxysilane were stirred at low speed at 5rpm Mix uniformly for 30min, then add the remaining plasticizer PPG1000 and reinforcing resin, stir at 8rpm for 35min under vacuum condition of -0.098MPa, and degassing to obtain the single-component silane-modified polyether sealant.

Example 6

The reinforcing resin has the following structural features:

Wherein, the ratio of m to n is 2:1, and R is ethyl.

The preparation method of the reinforced resin comprises the following steps:

(1) Add polyetheramine D400 into the reaction kettle, according to the molar ratio of polyetheramine D400 and epoxy resin E51 to be 1:0.9, slowly add epoxy resin E51 under low-speed stirring, heat up to 58°C, and react for 6h to obtain Modified epoxy resin;

(2) slowly heating the reaction kettle to 120°C, according to the ratio of the mole number of ethyltrimethoxysilane to the mole number of hydroxyl groups in the modified epoxy resin, 1:0.8, to the modified epoxy resin of step (1) Ethyltrimethoxysilane was added, and then a catalyst, dibutyltin dilaurate, was added dropwise, and the reaction was stirred under vacuum for 4 hours to obtain the reinforced resin.

Wherein, the addition amount of catalyst dibutyltin dilaurate is 0.3% of the mass of ethyltrimethoxysilane.

Silane-modified polyether resin Germany Wacker STP-E30, rheology agent BYK-410, stabilizer B75, part of plasticizer PPG2000 (20 parts) and water scavenger vinylmethyldimethoxysilane were mixed at 15rpm. Stir at a low speed for 50 minutes and mix evenly, then add the remaining plasticizer PPG2000 and reinforced resin, stir at a speed of 10 rpm for 15 minutes under -0.09MPa vacuum condition, and degassing to obtain the one-component silane-modified polyether sealant .

Comparative Example 1

In this comparative example, a one-component silane-modified polyether sealant is provided, and the preparation raw materials of the one-component silane-modified polyether sealant, in parts by weight, include the following components:

The difference between this comparative example and Example 1 is that the preparation raw materials do not include reinforcing resin, the weight part of silane-modified polyether resin (WACKER STP-E10, Germany) is 65 parts, and 2 parts of amino silane are used for coupling Agent KH550 was used as the catalyst, and the rest were the same as in Example 1.

Comparative Example 2

The difference between this comparative example and Example 2 is that the preparation raw materials do not include reinforcing resin, the weight part of silane-modified polyether resin (WACKER STP-E30, Germany) is 57 parts, and 1 part of amino silane is used for coupling Agent KH540 was used as the catalyst, and the rest were the same as in Example 2.

Comparative Example 3

The difference between this comparative example and Example 3 is that the preparation raw materials do not include reinforcing resin, the weight parts of silane-modified polyether resin (German Wacker STP-E30) is 43 parts, and the weight of plasticizer (PPG4000) is 43 parts by weight. The number of parts is 50 parts, and 0.5 part of aminosilane coupling agent KH792 is used as a catalyst, and the rest are the same as in Example 3.

Comparative Example 4

Silane-modified polyether resin STP-E10, silane-modified polyether resin STP-XB502, part of plasticizer PPG3000 (10 parts), fumed silica HDK H18, stabilizer B75 and water scavenger vinyl trimethoxy Silane, stir at a low speed of 10rpm for 60min and mix well, add the remaining plasticizer PPG3000 and aminosilane coupling agent KH540, under -0.095MPa vacuum condition, stir at a speed of 5rpm for 30min, defoaming to obtain the single group Silane-modified polyether sealant.

The performance test of the one-component silane-modified polyether sealants prepared in Examples 1-6 and Comparative Examples 1-4 is as follows:

(1) Surface dry time: Test according to GB/T 13477.5-2003, under the conditions of (23±2)℃, (50±10)%RH, squeeze the adhesive strip on a clean glass plate, use it every 1min Touch the surface of the glue with your fingers, and the time until it does not stick to the hand is the dry time;

(2) Hardness: test according to GB/T 531-1999;

(3) Tensile strength and elongation at break: test according to GB/T 528-2009, place the mold on the PE film, inject the sealant into the mold with a glue gun, smooth it with a scraper, and remove the excess sealant , Remove the mold from the film, the thickness of the adhesive layer is 2.5-3.0mm, put it at a temperature of (23 ± 2) ° C, (50 ± 10)% RH for curing and curing for 7 days, take out the film, and cut it into the specified size The dumbbell-shaped test piece was tested at room temperature tensile strength and elongation at break at a tensile speed of 500mm/min;

(4) Tensile shear strength: Tested according to GB/T 7124-2008, the lap length of the standard sample is (10.0±0.5) mm, the thickness of the adhesive layer is 0.2 mm, and the bonding substrate is anodized Aluminum, wipe it clean with ethyl acetate, dry it at 105-110℃, put it in a desiccator for later use, after bonding the test piece with glue, it needs to be at (23±2)℃, (50±10)%RH conditions Test after curing and curing for 7 days, and record the failure type (CF: cohesive failure, AF: interface failure) according to the regulations in GB/T 16997;

(5) Transparency: test according to GB/T2410-2008, use SM-2 type light transmittance tester to test the light transmittance of the sealant, and the film thickness is 2mm.

The performance test results are shown in Table 1.

Table 1

As can be seen from Table 1, compared with Comparative Examples 1-4, the sealants prepared in Examples 1-6 can be cured without adding an aminosilane coupling agent, and the cured mechanical strength (tensile strength: 5.3-8.8 MPa, tensile shear strength: 4.1-7.3MPa) and transparency (transmittance: 92-93%) are significantly improved, meeting the requirements of high strength and high transparency of silane-modified polyether sealants, that is, according to GB/T 528-2009 test tensile strength>5Mpa, according to GB/T2410-2008 test light transmittance>85%.

The applicant declares that the present invention illustrates the one-component silane-modified polyether sealant of the present invention and its preparation method and application through the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention must Implementation depends on the above-mentioned embodiment. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

A one-component silane-modified polyether sealant, characterized in that the preparation raw materials of the one-component silane-modified polyether sealant, in parts by weight, include the following components:

The reinforcing resin has the following structural features:

Wherein, m, n are integers and 1≤m≤50, 1≤n≤25, the ratio of m to n is (1～2):1, R is any one of methyl, ethyl or phenyl or A combination of at least two.
The one-component silane-modified polyether sealant according to claim 1, wherein the silane-modified polyether resin is a silane-modified polyether resin end-capped with α-silane, and has the following structural features:

Wherein, Me is methyl;

Preferably, the silane-modified polyether resin includes any one or a combination of at least two of STP-E10 resin, STP-E30 resin or STP-XB502 resin produced by Wacker, Germany.
The one-component silane-modified polyether sealant according to claim 1 or 2, wherein the preparation method of the reinforced resin comprises the following steps:

(1) adding epoxy resin to polyetheramine, heating up, and reacting to obtain modified epoxy resin;

(2) heating up, adding trialkoxysilane to the modified epoxy resin in step (1), then adding a catalyst, and performing a vacuum stirring reaction to obtain the reinforced resin.
The one-component silane-modified polyether sealant according to claim 3, wherein the polyetheramine is a difunctional polyetheramine;

Preferably, the molecular weight of the polyetheramine is 100-3000;

Preferably, the polyetheramine comprises any one or a combination of at least two of Huntsman D230, D400 or D2000;

Preferably, the epoxy resin is a bisphenol A epoxy resin;

Preferably, the molecular weight of the epoxy resin is 600-5000;

Preferably, the epoxy resin comprises any one or a combination of at least two of commercially available E44, E51 or E35;

Preferably, the trialkoxysilane includes alkyltrialkoxysilane and/or aryltrialkoxysilane, preferably methyltrimethoxysilane, ethyltrimethoxysilane or phenyltrimethoxysilane Any one or a combination of at least two, preferably methyltrimethoxysilane;

Preferably, the catalyst comprises dibutyltin dilaurate.
The one-component silane-modified polyether sealant according to claim 3 or 4, characterized in that, adding epoxy resin to polyetheramine in step (1), the molar ratio of polyetheramine to epoxy resin is 1:(0.5～1.5);

Preferably, described in step (2), add trialkoxysilane to the modified epoxy resin of step (1), and the ratio of the mole number of trialkoxysilane to the mole number of hydroxyl groups in the modified epoxy resin is 1: (0.1～1);

Preferably, the added amount of the catalyst is 0.1-1% of the mass of the trialkoxysilane.
The one-component silane-modified polyether sealant according to any one of claims 3-5, characterized in that, the temperature in step (1) is elevated to 50-60° C.;

Preferably, the reaction time of step (1) is 4-8h;

Preferably, the temperature increase in step (2) is to increase the temperature to 80-120°C;

Preferably, the time of the vacuum stirring reaction in step (2) is 1-6h.
The one-component silane-modified polyether sealant according to any one of claims 1-6, wherein the plasticizer comprises any of polyether polyols PPG1000, PPG2000, PPG3000, PPG4000 or PPG8000 one or a combination of at least two;

Preferably, the rheological agent is a liquid thixotropic agent, preferably BYK-410 from Germany;

Preferably, the stabilizer is a liquid stabilizer, preferably BASF B75;

Preferably, the water scavenger is a vinyl functional silane type water scavenger, including any one or at least one of vinyltrimethoxysilane, vinyltriethoxysilane or vinylmethyldimethoxysilane combination of the two.
The preparation method of the one-component silane-modified polyether sealant according to any one of claims 1-7, wherein the preparation method comprises the following steps:

Mix the silane-modified polyether resin, rheology agent, stabilizer, part of plasticizer and water scavenger evenly, then add the remaining plasticizer and reinforcing resin, stir under vacuum conditions, and defoaming to obtain the monolayer. Components Silane-modified polyether sealant.
preparation method according to claim 8, is characterized in that, the rotating speed of described mixing is 5-15rpm, and the time of mixing is 20-60min;

Preferably, the vacuum degree of the vacuum condition is -0.09～-0.1MPa;

Preferably, the stirring speed is 5-10 rpm, and the stirring time is 15-60 min.
Application of the one-component silane-modified polyether sealant according to any one of claims 1 to 7 in interior decoration, automobile windshield or locomotive structural bonding.