WO2023160197A1

WO2023160197A1 - Single-component organic silicon-modified sealant capable of being rapidly deep-layer cured at low temperature, and preparation method therefor

Info

Publication number: WO2023160197A1
Application number: PCT/CN2022/141393
Authority: WO
Inventors: 陈洋庆; 陈建军; 黄恒超; 高敏华; 唐华
Original assignee: 广州市白云化工实业有限公司; 广东白云科技有限公司
Priority date: 2022-02-23
Filing date: 2022-12-23
Publication date: 2023-08-31
Also published as: CN114479741A; CN114479741B

Abstract

The present invention discloses a single-component organic silicon-modified sealant and a preparation method therefor. The single-component organic silicon-modified sealant is prepared from the following raw materials: 15 to 40 parts of a trimethoxy silane-terminated polyurea resin, 20 to 50 parts of a reinforcing filler, 3 to 10 parts of a functional filler and 10 to 50 parts of a plasticizer, 0.2 to 1.5 parts of a humectant, 0.1 to 2 parts of a rheological agent, 0.5 to 2 parts of a stabilizer, 0.5 to 2 parts of a water removal agent, 0.5 to 2 parts of a coupling agent, and 0.1 to 3 parts of a catalyst. The functional filler is surface-modified calcium oxide. The deep-layer curing depth of the single-component organic silicon-modified sealant at a low temperature (about 0°C) within 24 hours is greater than or equal to 3 mm, and has good mechanical property after curing.

Description

One-component organosilicon-modified sealant capable of fast deep curing at low temperature and preparation method thereof

The present invention requires a Chinese patent application submitted to the China Patent Office on February 23, 2022, with the application number 202210167533.3, and the title of the application is "A One-Component Silicone Modified Sealant with Rapid Deep Curing at Low Temperature and Its Preparation Method" priority, the entire contents of which are incorporated herein by reference.

technical field

The invention relates to the field of sealants, in particular to a one-component organosilicon-modified sealant capable of fast deep curing at low temperature and a preparation method thereof.

Background technique

The traditional one-component silicone sealant and silane-modified polyether sealant (MS glue) are a kind of catalyst, which is initiated by moisture in the air and undergoes a cross-linking reaction under certain conditions to form a high Adhesive sealing products with molecular network structure. Under normal circumstances, the silane-modified polyether adhesive with better deep curing has a 24h curing depth (thickness) of 3-4mm, while the 24h curing depth of silicone adhesive is only about 1-2mm. It can be seen that the one-component silicone sealant The fastest 24h curing depth is generally about 4mm, and the curing of one-component silicone sealant is from the surface to the inside, which is significantly affected by the external environment. When the temperature is low, the surface dries slowly, and when the temperature is high, the surface dries quickly. When the activity of the catalyst is low, the moisture curing reaction speed is very slow, resulting in a slow curing speed of the one-component silicone sealant, especially when the temperature in northern China is low in winter (about 0-5 ° C), silane modified polyether The glue curing speed is only about 1mm, or even lower. If a larger glue curing depth (thickness) is required, it often takes a very long time, which brings great inconvenience to the construction operation, which also limits it to a certain extent. Application of one-component silicone sealants.

Contents of the invention

In view of the above problems, the present invention provides a one-component silicone modified sealant that can be cured quickly and deeply at low temperature. 3mm, and the mechanical properties after curing are good. The present invention includes the following technical solutions.

A one-component silicone modified sealant prepared in parts by weight from raw materials comprising the following components:

The functional filler is surface-modified calcium oxide.

In some of these embodiments, the one-component silicone modified sealant is prepared from raw materials including the following components:

In some embodiments, the trimethoxysilane-terminated polyurea resin is obtained by reacting polyurea prepolymer and aminotrimethoxysilane, and the polyurea prepolymer is obtained by reacting polyetheramine and diisocyanate.

In some of the embodiments, the molar ratio of the amine groups in the polyetheramine to the NCO groups in the diisocyanate is 1:1.2-1.5.

In some of the embodiments, the molar ratio of NCO groups and aminotrimethoxysilane in the polyurea prepolymer is 1:0.8-1.2.

In some of the embodiments, the polyetheramine has a molecular weight of 100-3000.

In some of the embodiments, the polyetheramine is selected from at least one of D230, D400 and D2000 manufactured by Huntsman, USA.

In some of these embodiments, the diisocyanate is selected from hexamethylene diisocyanate (HDI), diphenylmethane-4,4'-diisocyanate (MDI), IPDI trimer and toluene diisocyanate (TDI) at least one of the

In some of the embodiments, the molecular weight of the aminotrimethoxysilane is 100-2000.

In some of these embodiments, the aminotrimethoxysilane is selected from γ-aminopropyltrimethoxysilane (KH-540), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792) and at least one of anilinomethyltrimethoxysilane (coupling agent NANDA-73).

In some of these embodiments, the preparation method of the trimethoxysilane-terminated polyurea resin comprises the following steps:

(1) Add polyetheramine into the reaction kettle, then add diisocyanate, and react for 2h-4h under the protection of nitrogen or inert gas to obtain polyurea prepolymer;

(2) Under the protection of nitrogen or inert gas, add aminotrimethoxysilane to the polyurea prepolymer, stir and react for 2h-4h, and obtain the trimethoxysilane-terminated polyurea resin.

In some of the embodiments, the surface-modified calcium oxide is selected from at least one of stearic acid-modified calcium oxide, silane coupling agent-modified calcium oxide and titanate-modified calcium oxide.

In some of these embodiments, the calcium oxide modified by the silane coupling agent is calcium oxide modified by γ-methacryloxypropyltrimethoxysilane; the calcium oxide modified by titanate is Calcium oxide modified with isopropyl triisostearate titanate.

In some of the embodiments, the preparation method of the surface-modified calcium oxide comprises the following steps: react calcium oxide and a surface modifier in an organic solvent, filter, and dry to obtain the product.

In some of these embodiments, the surface modifier is selected from at least one of stearic acid, silane coupling agent and titanate, more preferably stearic acid, γ-methacryloxypropyl At least one of trimethoxysilane and isopropyl triisostearate titanate.

In some of these embodiments, the surface modifier is 3-10% of the mass of calcium oxide.

In some of these embodiments, the organic solvent is toluene.

In some of these embodiments, the temperature of the reaction is 30° C.-40° C., and the reaction time is 0.5 hours-1.5 hours.

In some of these embodiments, the humectant is a polyol type humectant.

In some of the embodiments, the polyhydric alcohol moisturizing agent is selected from at least one of glycerin, polyethylene glycol and butylene glycol.

In some of the embodiments, the reinforcing filler is selected from at least one of nano-active calcium carbonate, silica micropowder, ground calcium carbonate or talcum powder.

In some of the embodiments, the plasticizer is selected from at least one of dioctyl phthalate, dioctyl adipate, diphenyl-isooctyl phosphate and polypropylene glycol.

In some of the embodiments, the rheological agent is selected from at least one of polyamide wax, hydrogenated castor oil, organic bentonite and fumed silica.

In some of these embodiments, the stabilizer is BASF light stabilizer 770, BASF light stabilizer 328 and/or BASF light stabilizer 326.

In some of these embodiments, the water-removing agent is a silane-based water-removing agent containing a vinyl functional group, for example, it can be vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxy silanes or their mixtures.

In some of the embodiments, the coupling agent is an aminosilane coupling agent, for example, it can be at least one of Dow Corning KH-540, KH-550, KH-792 and KH-560.

In some of the embodiments, the catalyst is selected from at least one of dibutyltin dilaurate, dioctyltin diacetate and stannous octoate.

The trimethoxysilane-terminated polyurea resin is obtained by reacting polyurea prepolymer and anilinomethyltrimethoxysilane, and the polyurea prepolymer is obtained by reacting polyetheramine D2000 and IPDI trimer. The molar ratio of the amine group in polyetheramine D2000 to the NCO group in the IPDI trimer is 1:1.2-1.3, and the molar ratio of the NCO group in the polyurea prepolymer to aminotrimethoxysilane is 0.95-1.05;

The reinforcing filler is a combination of nano active calcium carbonate and ground calcium carbonate with a mass ratio of 1-2:1;

The titanate-modified calcium oxide is calcium oxide modified with isopropyl titanate triisostearate.

The present invention also provides the preparation method of the above-mentioned one-component silicone modified sealant, which includes the following technical solutions.

A preparation method of the above-mentioned one-component silicone modified sealant, comprising the steps of:

Put the trimethoxysilane-terminated polyurea resin, reinforcing filler, functional filler, rheological agent, stabilizer, humectant and part of plasticizer at a temperature of 100°C-130°C and a vacuum degree of -0.09MPa～ Kneading for 1 hour to 3 hours under the condition of -0.1MPa to obtain the base material;

After cooling the base material to a temperature lower than 50°C, add the remaining plasticizer, water remover, coupling agent and catalyst in sequence, and stir for 0.5 hours under the condition of vacuum degree of -0.09MPa～-0.1MPa- After 1 hour, the material was discharged to obtain the one-component silicone modified sealant.

A kind of one-component organosilicon-modified sealant prepared by the present invention that can be cured quickly and deeply at low temperature is based on trimethoxysilane-terminated polyurea resin as a base polymer, and surface modified and oxidized with a humectant and a functional filler. Calcium filler, rheological agent, etc. are used as auxiliary materials, and the ratio of each component is adjusted reasonably. It has the following characteristics and advantages:

(1) Compared with the traditional silicone resin (silane-modified polyether polymer, 107 glue), the silane-terminated polyurea resin of the present invention is a trimethoxysilane-terminated urea-based polymer, similar to the chain end structure , compared with dimethoxysilane, triethoxysilane or other alkoxysilane-terminated polyurea resins, trimethoxysilane-terminated polyurea resins have stronger hydrolysis activity, and due to the electron-pushing group in the structure

The inductive effect is strong, which can greatly enhance the hydrolysis and polymerization activity of alkoxy groups, thereby accelerating the curing speed and crosslinking density of the sealant system.

(2) Adding a humectant can provide the silicone sealant system in a low temperature environment with the moisture required for the moisture curing reaction, thereby maintaining the deep curing reaction speed.

(3) Compared with traditional silicone sealants such as silane-modified polyether glue and silicone glue, the single-component silicone-modified sealant of the present invention, which can be quickly and deeply cured at low temperature, has added surface-modified calcium oxide As a functional filler, on the one hand, the modified calcium oxide can be well compatible with the sealant system; on the other hand, calcium oxide is easy to react with water and release a lot of heat to increase the surface temperature of the sealant, thereby increasing the catalytic activity. Reactivity, accelerate the deep reaction rate of moisture curing, solve the problem of slow curing rate of silicone sealant at low temperature, thereby expanding the scope of use.

(4) The one-component organosilicon modified sealant of the present invention is matched with other auxiliary materials such as the above-mentioned trimethoxysilane-terminated polyurea resin, humectant and surface-modified calcium oxide filler as a functional filler in an appropriate proportion. , the heaviest makes it have the advantages of fast curing speed at low temperature, the deep curing depth ≥ 3mm within 24 hours at low temperature (about 0 ℃), and the mechanical properties after curing are good.

Detailed ways

The technical solutions of the present invention will be further described below through specific examples. It should be clear to those skilled in the art that the examples are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the technical field of the present invention. Terms used in the description of the present invention are only for the purpose of describing specific embodiments, and are not used to limit the present invention.

The terms "including" and "having" and any variations thereof in the present invention are intended to cover a non-exclusive inclusion. For example, a process, method, device, product or equipment that includes a series of steps is not limited to the listed steps or modules, but optionally also includes steps that are not listed, or optionally also includes for these processes, Other steps inherent in a method, product, or apparatus.

The "plurality" mentioned in the present invention means two or more. "And/or" describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B may indicate: A exists alone, A and B exist simultaneously, and B exists independently. The character "/" generally indicates that the contextual objects are an "or" relationship.

The following are specific examples.

Example 1

The one-component silicone-modified sealant provided in this example is prepared from the following raw materials in parts by weight:

The preparation method of described trimethoxysilane-terminated polyurea resin is as follows:

(1) Add polyetheramine D230 (its molecular weight is 230) into the reaction kettle, and slowly add di Isocyanate HDI was reacted at room temperature for 3 hours under the protection of nitrogen to obtain polyurea prepolymer (PUA).

(2) Under nitrogen protection, add aminotrimethoxysilane (KH-540) to the PUA prepared in step 1 according to the molar ratio of NCO to aminotrimethoxysilane of 1:0.8, and stir at low speed for about 3 hours at room temperature until the The di-n-butylamine back-titration method detects that no isocyanate group exists in the reaction system, and the reaction is terminated, and a trimethoxysilane-terminated polyurea resin is obtained.

The preparation method of the calcium oxide of described hard fatty acid surface modification comprises the following steps:

Add CaO and 3% stearic acid whose mass is CaO into a reaction kettle filled with toluene that is half of the mass of CaO, stir and react at 15 rpm for 1.5 hours at 30°C, and extract it with an organic filter to obtain The solid sample is dried and then ground into powder to obtain hard fatty acid modified calcium oxide.

The preparation method of the one-component organosilicon-modified sealant that can be cured rapidly and deeply at low temperature in this embodiment includes the following steps:

Described trimethoxysilane terminated polyurea resin, reinforcing filler (nano active calcium carbonate), functional filler (hard fatty acid modified calcium oxide), rheological agent (fumed white carbon black), stabilizer, humectant ( Glycerin), 25 parts of plasticizer (dioctyl phthalate) were kneaded for 2 hours at a temperature of 100°C and a vacuum of -0.09MPa to obtain a base material;

After cooling the base material to a temperature lower than 50°C, add the remaining plasticizer, water remover (vinyltriethoxysilane), coupling agent (KH-540) and catalyst (dilauric acid di Butyl tin), stirred for 0.5 hour under the condition of vacuum degree of -0.09MPa, and discharged to obtain the one-component silicone-modified sealant that can be cured quickly and deeply at low temperature.

Example 2

(1) Add polyetheramine D400 (its molecular weight is 400) into the reaction kettle, and slowly add di Isocyanate MDI was reacted at room temperature for 3 hours under the protection of nitrogen to obtain polyurea prepolymer (PUA).

(2) Under the protection of nitrogen, add aminotrimethoxysilane (KH-792) to the PUA prepared in step 1 according to the molar ratio of NCO to aminotrimethoxysilane of 1:1.2, and stir at low speed for about 3 hours at room temperature until The di-n-butylamine back-titration method detects that no isocyanate group exists in the reaction system, and the reaction is terminated, and a trimethoxysilane-terminated polyurea resin is obtained.

Wherein the preparation method of the calcium oxide modified by silane coupling agent comprises the following steps:

Add CaO and 10% γ-methacryloxypropyl trimethoxysilane (KH-570) whose mass is CaO to a reaction kettle filled with toluene, which is half of the mass of CaO, at 40°C, Stir and react at 25rpm for 0.5h, extract the solid sample with an organic filter membrane, and grind it into powder after drying to obtain silane coupling agent modified calcium oxide.

Described trimethoxysilane terminated polyurea resin, reinforcing filler (talcum powder), functional filler (silane coupling agent modified calcium oxide), rheological agent (polyamide wax), stabilizer, humectant (butylene diol), 15.5 parts of plasticizer (PPG3000) at a temperature of 110°C and a vacuum of -0.1MPa, and kneaded for 3 hours to obtain a base material;

After cooling the base material to a temperature lower than 50°C, add the remaining 5 parts of plasticizer, water remover (vinyltrimethoxysilane), coupling agent (KH-550) and catalyst (diacetate diacetate) in sequence. octyltin), stirred for 1 hour under the condition of vacuum degree of -0.1MPa, and discharged to obtain the one-component silicone modified sealant that can be cured quickly and deeply at low temperature.

Example 3

(1) Add polyetheramine D2000 (its molecular weight is 2000) into the reaction kettle, and slowly add di Isocyanate IPDI was reacted at room temperature for 3 hours under the protection of nitrogen to obtain polyurea prepolymer (PUA).

(2) Under nitrogen protection, add aminotrimethoxysilane (Nanda-73) to the PUA prepared in step 1 according to the molar ratio of NCO and aminotrimethoxysilane at 1:1, and stir at low speed for about 3 hours at room temperature until it is used The di-n-butylamine back-titration method detects that no isocyanate group exists in the reaction system, and the reaction is terminated, and a trimethoxysilane-terminated polyurea resin is obtained.

The calcium oxide modified by titanate comprises the following steps:

After adding CaO and 5% isopropyl triisostearate titanate whose mass is CaO into a reaction kettle filled with toluene that is half of the mass of CaO, stir and react at 20 rpm for 1 h at 35°C, organic The solid sample is obtained after the filter membrane is extracted, dried and then ground into powder to obtain titanate-modified calcium oxide.

The trimethoxysilane terminated polyurea resin, reinforcing filler (nano active calcium carbonate and heavy calcium carbonate), functional filler (titanate modified calcium oxide), rheology agent (hydrogenated castor oil), stabilizer agent, humectant (polyethylene glycol), and 10 parts of plasticizer (diphenyl-isooctyl phosphate) were kneaded for 3 hours at a temperature of 110°C and a vacuum of -0.1MPa to obtain a base material;

After cooling the base material to a temperature below 50°C, add the remaining 4.5 parts of plasticizer, water remover (vinyltrimethoxysilane), coupling agent (KH-792) and catalyst (stannous octoate ), stirred for 1 hour under the condition of vacuum degree of -0.09MPa, and discharged to obtain the one-component silicone-modified sealant that can be cured quickly and deeply at low temperature.

Comparative example 1:

The difference between the one-component silicone-modified sealant provided in this comparative example and the one-component silicone modified sealant that can be cured rapidly at low temperature and that in Example 1 is that the trimethoxysilane in Example 1 is replaced by triethoxysilane-terminated polyurea resin The blocked polyurea resin is specifically prepared from the following raw materials in parts by weight:

The preparation method of described triethoxysilane-terminated polyurea resin is as follows:

(2) Add γ-aminopropyltriethoxysilane (KH550) to the PUA prepared in step 1 under the protection of nitrogen according to the molar ratio of NCO to γ-aminopropyltriethoxysilane of 1:0.8, at room temperature The reaction was stirred at a low speed for about 3 hours, and the reaction was terminated when no isocyanate groups existed in the reaction system as measured by back titration with di-n-butylamine, and a triethoxysilane-terminated polyurea resin was obtained.

The preparation method of the one-component organosilicon-modified sealant that can be cured rapidly and deeply at low temperature in this comparative example comprises the following steps:

Described triethoxysilane-terminated polyurea resin, reinforcing filler (nano active calcium carbonate), functional filler (hard fatty acid modified calcium oxide), rheology agent (fumed white carbon black), stabilizer, humectant (glycerol), 25 parts of plasticizer (dioctyl phthalate) at a temperature of 100°C and a vacuum of -0.09MPa, kneading for 2 hours to obtain a base material;

Comparative example 2:

The difference between the one-component silicone modified sealant provided in this comparative example that can be cured quickly and deeply at low temperature and Example 2 is that no silane coupling agent is added to modify calcium oxide, and it is specifically prepared from the following raw materials in parts by weight :

Described trimethoxysilane terminated polyurea resin, reinforcing filler (talcum powder), rheological agent (polyamide wax), stabilizer, humectant (butylene glycol), 15.5 parts of plasticizer (PPG3000) at temperature Under the conditions of 110°C and vacuum degree of -0.1MPa, knead for 3 hours to obtain the base material;

Comparative example 3

The one-component silicone-modified sealant provided in this comparative example that can be cured quickly and deeply at low temperature is different from Example 3 in that no humectant is added, and it is specifically prepared from the following raw materials in parts by weight:

The calcium oxide modified by titanate comprises the following steps:

The trimethoxysilane terminated polyurea resin, reinforcing filler (nano active calcium carbonate and heavy calcium carbonate), functional filler (titanate modified calcium oxide), rheology agent (hydrogenated castor oil), stabilizer Agent, 10 parts of plasticizer (diphenyl-isooctyl phosphate) were kneaded for 3 hours at a temperature of 110°C and a vacuum of -0.1MPa to obtain a base material;

After cooling the base material to a temperature below 50°C, add the remaining 4.5 parts of plasticizer, water remover (vinyltrimethoxysilane), coupling agent (KH-792) and catalyst (stannous octoate ), stirred for 1 hour under the condition of vacuum degree of -0.1MPa, and discharged to obtain the one-component silicone modified sealant that can be quickly and deeply cured at low temperature.

Comparative example 4

Select the silane-modified polyether adhesive 331 produced by a company with a better curing depth on the market.

A low-temperature fast deep-curable one-component silicone modified sealant prepared in Examples 1-3 and Comparative Examples 1-4 was subjected to the following performance test. The test method is as follows:

Deep curing: Put the samples prepared in Examples 1-3 and Comparative Examples 1-4 in accordance with GB/T 32369-2015 "Determination of Curing Degree of Sealant" Appendix A curing cup method respectively placed at ①23℃, 50%RH,②0℃ , ③-10 ℃ three conditions to test the curing depth of 24h.

Surface drying time: according to GB/T 13477.5-2003 test. Under the conditions of (23±2)℃, (50±10)%RH, squeeze the adhesive strip on a clean glass plate, touch the surface of the adhesive with your fingers every 1min, and the time until it is not sticky is the surface dry time .

Hardness: Tested according to GB/T 531-1999.

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

Tensile shear strength: tested according to GB/T 7124-2008. The lap length of the standard sample is (10.0±0.5)mm, and the thickness of the adhesive layer is 0.2mm. The bonding substrate is anodized aluminum, wipe it clean with ethyl acetate, dry it at 105-110°C, and put it in a desiccator for later use. After the test piece is bonded with glue, it needs to be cured and cured for 7 days under the conditions of (23±2)℃, (50±10)%RH, then tested, and the failure type should be recorded according to the regulations in GB/T 16997 (CF: cohesive failure, AF: interface failure).

Table 1: 24h sealant deep curing test results (mm/24h)

Table 2: Basic Mechanical Properties Test Results

From the experimental results in Table 1, it can be seen that the sealants prepared in Examples 1-3 and Comparative Examples 1-4 have good curing rates at 23°C and 50% RH, and the curing depths are all above 4mm in 24 hours. , but under the condition of 0°C, the one-component silicone modified sealant prepared in Example 1-3, the 24h curing depth can reach more than 3.3mm, which is better than the 24h curing depth of Comparative Example 1-4 (all <3mm ), compared with Examples 1-3 and Comparative Examples 1-3, the conventional silane-modified polyether glue sold in the market in Comparative Example 4 is only 1.27mm, and the curing rate is slow, thereby limiting its use, which also illustrates the use The silane-terminated polyurea polymer prepared by the invention has higher activity. Under the condition of -10°C, the one-component silicone modified sealant prepared in Example 1-3 can still reach a curing depth of more than 1.2 mm in 24 hours, and the one-component silicone modified sealant prepared in Example 3, Its 24h curing depth can still be close to 2mm, indicating that it still has good deep-layer curing ability in a low temperature environment of -10°C; while the one-component silicone modified sealant prepared in Comparative Examples 1-4, its 24h curing depth All < 1mm, the conventional silane-modified polyether glue on the market is only 0.38mm.

The mechanical results in Table 2 show that compared with the conventional silane-modified polyether adhesives on the market, the silicone-modified sealant prepared by the present invention also has better mechanical properties. Therefore, the fast deep-curing one-component silicone sealant prepared by the present invention has a curing depth of >3 mm in 24 hours no matter at normal temperature or low temperature (0° C.). After complete curing, it also has good mechanical properties, even -10 ℃ still has a 24h curing depth of more than 1.2mm (equivalent to the 24h curing depth of silicone adhesives in general), thus expanding the use of silicone sealants in low temperature environments.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims

A one-component silicone modified sealant is characterized in that, in parts by weight, it is prepared from raw materials comprising the following components:

The functional filler is surface-modified calcium oxide.
The one-component silicone modified sealant according to claim 1, characterized in that, it is prepared from raw materials comprising the following components:
The one-component silicone modified sealant according to claim 1, wherein the trimethoxysilane-terminated polyurea resin is obtained by reacting a polyurea prepolymer and aminotrimethoxysilane, and the polyurea resin is Urea prepolymers are obtained by reacting polyetheramines with diisocyanates.
The one-component silicone modified sealant according to claim 3, wherein the molar ratio of the amine group in the polyetheramine to the NCO group in the diisocyanate is 1:1.2-1.5; and/ or,

The molar ratio of NCO groups and aminotrimethoxysilane in the polyurea prepolymer is 1:0.8-1.2; and/or,

The molecular weight of the polyetheramine is 100-3000; and/or,

The molecular weight of the aminotrimethoxysilane is 100-2000.
The one-component silicone modified sealant according to claim 4, wherein the polyetheramine is selected from at least one of D230, D400 and D2000 of Huntsman Corporation of the United States; and/or,

The diisocyanate is selected from at least one of hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, IPDI trimer and toluene diisocyanate; and/or,

The aminotrimethoxysilane is selected from at least one of γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and anilinomethyltrimethoxysilane kind.
The single-component silicone modified sealant according to claim 3, wherein the preparation method of the trimethoxysilane-terminated polyurea resin comprises the steps of:

(1) Add polyetheramine into the reaction kettle, then add diisocyanate, and react for 2h-4h under the protection of nitrogen or inert gas to obtain polyurea prepolymer;

(2) Under the protection of nitrogen or inert gas, add aminotrimethoxysilane to the polyurea prepolymer, stir and react for 2h-4h, and obtain the trimethoxysilane-terminated polyurea resin.
The one-component silicone modified sealant according to any one of claims 1-6, wherein the surface-modified calcium oxide is selected from stearic acid-modified calcium oxide, silane coupling agent modified At least one of permanent calcium oxide and titanate-modified calcium oxide;

The calcium oxide modified by the silane coupling agent is the calcium oxide modified by gamma-methacryloxypropyltrimethoxysilane;

The titanate-modified calcium oxide is calcium oxide modified with isopropyl titanate triisostearate.
The single-component silicone modified sealant according to any one of claims 1-6, wherein the preparation method of the surface-modified calcium oxide comprises the steps:

The calcium oxide and the surface modifying agent are reacted in an organic solvent, filtered and dried to obtain the product.
The one-component silicone modified sealant according to claim 8, wherein the surface modifier is selected from at least one of stearic acid, silane coupling agent and titanate; and/or ,

The surface modifier is 3-10% of the mass of calcium oxide; and/or,

The organic solvent is toluene; and/or,

The reaction temperature is 30°C-40°C, and the reaction time is 0.5 hours-1.5 hours.
The one-component silicone modified sealant according to claim 9, wherein the surface modifier is selected from the group consisting of stearic acid, γ-methacryloxypropyl trimethoxysilane and triiso At least one of isopropyl stearate titanate.
The one-component silicone modified sealant according to any one of claims 1-6, characterized in that,

The humectant is a polyhydric alcohol humectant; and/or,

The reinforcing filler is selected from at least one of nano-active calcium carbonate, silicon micropowder, ground calcium carbonate or talcum powder; and/or,

The plasticizer is selected from at least one of dioctyl phthalate, dioctyl adipate, diphenyl-isooctyl phosphate and polypropylene glycol; and/or,

The rheological agent is selected from at least one of polyamide wax, hydrogenated castor oil, organic bentonite and fumed silica; and/or,

The stabilizer is BASF light stabilizer 770, BASF light stabilizer 328 and/or BASF light stabilizer 326; and/or,

The water removal agent is a silane water removal agent containing a vinyl functional group; and/or,

The coupling agent is an aminosilane coupling agent; and/or,

The catalyst is at least one selected from dibutyltin dilaurate, dioctyltin diacetate and stannous octoate.
The one-component silicone modified sealant according to claim 11, wherein the humectant is selected from at least one of glycerin, polyethylene glycol and butylene glycol; and/or,

The water remover is selected from at least one of vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldimethoxysilane; and/or,

The coupling agent is at least one selected from KH-540, KH-550, KH-792 and KH-560.
The one-component silicone modified sealant according to claim 1, characterized in that, it is prepared from raw materials comprising the following components:

The trimethoxysilane-terminated polyurea resin is obtained by reacting polyurea prepolymer and anilinomethyltrimethoxysilane, and the polyurea prepolymer is obtained by reacting polyetheramine D2000 and IPDI trimer. The molar ratio of the amine group in polyetheramine D2000 to the NCO group in the IPDI trimer is 1:1.2-1.3, and the molar ratio of the NCO group in the polyurea prepolymer to aminotrimethoxysilane is 1:0.95-1.05;

The reinforcing filler is a combination of nano active calcium carbonate and ground calcium carbonate with a mass ratio of 1-2:1;

The titanate-modified calcium oxide is calcium oxide modified with isopropyl titanate triisostearate.
A preparation method of the single-component silicone modified sealant according to any one of claims 1-13, characterized in that, comprising the steps of:

Put the trimethoxysilane-terminated polyurea resin, reinforcing filler, functional filler, rheological agent, stabilizer, humectant and part of plasticizer at a temperature of 100°C-130°C and a vacuum degree of -0.09MPa～ Kneading for 1 hour to 3 hours under the condition of -0.1MPa to obtain the base material;

After cooling the base material to a temperature lower than 50°C, add the remaining plasticizer, water remover, coupling agent and catalyst in sequence, and stir for 0.5 hours under the condition of vacuum degree of -0.09MPa～-0.1MPa- After 1 hour, the material was discharged to obtain the one-component silicone modified sealant.