CN114085641B - Silicone sealant and preparation method thereof - Google Patents
Silicone sealant and preparation method thereof Download PDFInfo
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- CN114085641B CN114085641B CN202111243251.9A CN202111243251A CN114085641B CN 114085641 B CN114085641 B CN 114085641B CN 202111243251 A CN202111243251 A CN 202111243251A CN 114085641 B CN114085641 B CN 114085641B
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- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- 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
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- 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
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- Sealing Material Composition (AREA)
Abstract
The invention discloses silicone sealant which comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane; 20-185 parts of filler; 9-22 parts of cross-linking agent; 1-2 parts of a coupling agent; 0.03-0.3 parts of catalyst; 3-25 parts of dimethyl silicone oil and branched silicone oil. According to the invention, by adopting the compounding of the dimethyl silicone oil and the branched silicone oil, the problem of oil seepage commonly existing in the oxime type silicone adhesive can be obviously improved.
Description
Technical Field
The invention relates to the technical field of adhesive materials, in particular to silicone sealant and a preparation method thereof.
Background
For more than 30 years, along with the continuous rapid development of national economy and the acceleration of urban process of China, the building curtain wall industry of China realizes the spanning development from none to all, the unified and universal foreign resources to the leading of domestic enterprises, the introduction of imitation to autonomous innovation, and the development of China to the beginning of 21 st century into the world production country and the use country of the curtain wall industry. From market application, along with the rapid promotion of the urban process of China, a huge number of large public buildings, commercial buildings and high-end residences are continuously emerging, and the large-scale public buildings, commercial buildings and high-end residences are important reasons for the rapid increase of the demand of the curtain wall of the China in recent years. Along with the high-speed development of building curtain walls, super high-rise building curtain walls are becoming more common, and the durability requirements for silicone sealants are also increasing.
In the prior art, the silicone sealant of an oxime type system generally has the problem of oil seepage (exuded oil is mainly a cross-linking agent), and the main reason is that the oxime type cross-linking agent has poor compatibility with alpha, omega-dihydroxy polydimethylsiloxane and simethicone. The existing improvement method mainly comprises the steps of adding an oil seepage resistant agent: for example, chinese patent application CN109652007a discloses an oil-repellent two-component silicone sealant in which the defect of bleeding out of methyl silicone oil is solved by using an oil-repellent agent (dodecanol ester compound or a mixture of dodecanol ester compounds). Chinese patent application CN105482769a discloses a plasticizer for silicone sealant, wherein silanized white oil is added as plasticizer, which improves the oil leakage phenomenon, but experiments show that the actual oil leakage problem of white oil is more serious.
Disclosure of Invention
The invention aims to provide a silicone sealant which has the advantage of no oil seepage.
The invention further provides a preparation method of the silicone sealant.
The invention is realized by the following technical scheme:
the silicone sealant comprises the following components in parts by weight:
the structural formula of the branched silicone oil is [ Me ] 3 SiO 0.5 ] a [Me 2 SiO] b [MeSi(OH)O] c Wherein 0 < c < 0.15, at a+b+c=1;
according to the weight ratio, the dimethyl silicone oil: branched silicone oil=5, (1 to 10).
Preferably, the weight ratio of the simethicone: branched silicone oil=5, (2.8 to 8.5).
The viscosity of the dimethyl silicone oil at 25 ℃ is 100-20000mpa.s; preferably, the viscosity of the simethicone is 350-12500mpa.s.
Preferably, the content of the simethicone and the branched silicone oil is 8-14 parts.
Preferably, in the branched silicone oil, c is more than 0.05 and less than 0.11.
The filler is at least one selected from calcium carbonate and fumed silica; preferably, the weight ratio of the calcium carbonate to the fumed silica is 20 (1-5). It has been found through experiments that fumed silica is effective in improving oil bleeding but that fumed silica is highly thickening and cannot be added in large amounts, and therefore, by using calcium carbonateThe combination of the main fumed silica and the auxiliary fumed silica can realize the balance of the overall performance and the improvement of the oil permeability. The invention has no special limitation on the particle size of calcium carbonate and fumed silica, and the particle size of the common calcium carbonate is in the range of 0.05-10 microns and the specific surface area of the fumed silica is 130-400m through experiments 2 Good technical results can be achieved in the range of/g.
The cross-linking agent is at least one selected from methyl tributyl ketoxime silane, vinyl tributyl ketoxime silane, propyl tributyl ketoxime silane, phenyl tributyl ketoxime silane, tetrabutyl ketoxime silane, methyl triacetonexime silane and vinyl triacetonexime silane.
The coupling agent is at least one selected from vinyl triethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl trimethoxysilane oligomer, vinyl triethoxysilane, oligomer of gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
The catalyst is at least one selected from dibutyl tin dilaurate, dibutyl tin diacetate and stannous octoate.
The preparation method of the silicone sealant provided by the invention comprises the following steps: uniformly mixing and stirring the alpha, omega-dihydroxyl polydimethylsiloxane, the dimethyl silicone oil, the branched silicone oil and the filler in parts by weight, stirring and dehydrating for 100-300min at 110-130 ℃ under the vacuum degree of 0.08-0.1 MPa, and cooling to obtain a base material; and then adding the base material into a planetary stirring kettle, adding a cross-linking agent, a coupling agent and a catalyst, and reacting for 30-80min under the vacuum degree of 0.06-0.1 MPa and the rotating speed of 200-800rpm to obtain the silicone sealant.
The invention has the following beneficial effects:
according to the invention, by adopting the compounding of the dimethyl silicone oil and the branched silicone oil, a certain amount of hydroxyl groups are contained in the branched silicone oil, and chemical bonds or hydrogen bonds can be formed between the branched silicone oil and the terminal hydroxyl groups or the cross-linking agent of the alpha, omega-dihydroxyl polydimethylsiloxane, so that the content of free ketoxime groups is reduced, and the oil seepage risk is reduced.
Secondly, the oil seepage phenomenon can be further improved through the preferable compound filler.
Drawings
Fig. 1: judging the oil seepage degree, wherein oil seepage is avoided, the white bottle body part is free from dark marks (oil marks formed by oil seepage), and oil-free beads are arranged on the black colloid;
fig. 2: judging the oil seepage degree, wherein the oil seepage is serious, the white bottle body part has a large number of continuous dark marks (oil marks formed by oil seepage), and the black colloid has obvious oil beads.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The raw materials used in the examples and comparative examples are as follows:
base polymer a: alpha, omega-dihydroxy polydimethylsiloxane having a viscosity at 25℃of 20000mpa.s available from Wake chemical (China);
base polymer B: alpha, omega-dihydroxy polydimethylsiloxane having a viscosity at 25℃of 50000mpa.s available from Michaelsen (Shanghai) trade Co., ltd;
dimethicone a: viscosity at 25 ℃ is 100mpa.s, available from simethicone B, a company of wack chemistry (china): viscosity 350mpa.s at 25 ℃ available from wack chemistry (china) limited;
dimethicone C: viscosity at 25 ℃ was 12500mpa.s, available from wack chemistry (china) limited;
dimethicone D: viscosity at 25 ℃ is 20000mpa.s, available from wack chemical (china) limited;
branched silicone oil a: c is 0.01, available from Jiangsu Co., ltd
Branched silicone oil B: c is 0.05, purchased from new Nazil materials science and technology Jiangsu Co., ltd;
branched silicone oil C: c is 0.11, purchased from new Nazil materials science and technology Jiangsu Co., ltd;
branched silicone oil D: c is 0.15, purchased from new Nazil materials science and technology Jiangsu Co., ltd;
calcium carbonate a: purchased from Kailong chemical Co., ltd., particle size range 0.05-1 μm;
calcium carbonate B: purchased from the coulong powder company, guangxi, city, particle size 1-10 microns.
Fumed silica: selected from cabot (China) investment Limited company, with specific surface area of 130-400m 2 /g。
Crosslinking agent A: methyl tributyl ketoximino silane available from Hubei New blue sky New Material Co., ltd
Crosslinking agent B: vinyl tributyl ketoximino silane, available from Hubei New blue sky New Material Co., ltd;
coupling agent A: gamma-aminopropyl triethoxysilane, available from fine chemicals, inc Jiang Han, state of the larch;
coupling agent B: gamma-glycidoxypropyl trimethoxysilane, available from fine chemical company, jiang Han, jingzhou;
catalyst: dibutyl tin dilaurate, available from Beijing-plus-chemostat, inc.
The testing method comprises the following steps:
(1) Oil permeability: the sealant was placed at 50 c for 20 days at 85% rh, and the sealant bottles were cut to see oil leakage from the bottom cap and the walls of the bottles, and the degree of oil leakage was evaluated according to the criteria of fig. 1-2 of the specification: FIG. 1 shows that oil seepage is avoided, a white bottle body part has no dark marks (oil marks), and oil-free beads are arranged on a black colloid (oil seepage is coagulated into beads); the slight oil seepage standard is that the white bottle body part has spotted dark marks, and the black colloid has no oil beads; the obvious oil seepage is that the white bottle body part has a small amount of continuous dark marks, and the black colloid is free of oil beads; the severe oil leakage is shown in fig. 2, the white bottle part has a large number of continuous dark, and the black colloid has obvious oil drops.
(2) Tensile modulus: the lower the tensile modulus, the better the test was performed as specified in GB/T13477.8-2017.
(3) Elongation at break: the test was performed as prescribed by 13477.8-2017.
Table 1: examples 1-6 Silicone sealants Each component content (parts by weight) and test results
As can be seen from examples 1-6, the preferred compounded fillers have better resistance to oil penetration and a low tensile modulus.
Table 2: examples 7-11 Silicone sealants Each component content (parts by weight) and test results
As is clear from examples 8 to 11, the addition amount of the simethicone and the branched silicone oil is preferable to lower the tensile modulus.
Table 3: examples 12-16 Silicone sealants Each component content (parts by weight) and test results
Examples 12-16 demonstrate that the preferred dimethicone/branched silicone oil formulations provide better oil barrier properties and lower tensile modulus.
Table 4: examples 17-22 Silicone sealants Each component content (parts by weight) and test results
As is evident from examples 14/17-22, the preferred simethicone viscosity and branched silicone oil structure have lower tensile modulus.
Table 5: examples 23-24 Silicone sealants Each component content (parts by weight) and test results
Table 7: comparative Silicone sealants each component content (parts by weight) and test results
Although the comparative example 4/5 also can obtain the technical effect of no oil seepage, the elongation at break is only 143% and 129%, the application value is very low, and the elongation at break is obviously lower than the breaking length (203% -325%) of the embodiment of the invention.
Claims (8)
1. The silicone sealant is characterized by comprising the following components in parts by weight:
100 parts of alpha, omega-dihydroxy polydimethylsiloxane;
20-185 parts of filler;
9-22 parts of cross-linking agent;
1-2 parts of a coupling agent;
0.03-0.3 parts of catalyst;
3-25 parts of total content of dimethyl silicone oil and branched silicone oil;
the structural formula of the branched silicone oil is [ Me ] 3 SiO 0.5 ] a [Me 2 SiO] b [MeSi(OH)O] c Wherein 0.05 < c < 0.11, at a+b+c=1;
according to the weight ratio, the dimethyl silicone oil: branched silicone oil=5, (2.8 to 8.5);
the filler is the compound of calcium carbonate and fumed silica, and the weight ratio is 20 (1-5).
2. The silicone sealant according to claim 1, wherein the viscosity of the dimethicone is 100-20000mpa.s at 25 ℃.
3. The silicone sealant according to claim 1, wherein the viscosity of the simethicone is 350-12500mpa.s.
4. The silicone sealant according to claim 1, wherein the total content of the simethicone and the branched silicone oil is 8 to 14 parts.
5. The silicone sealant according to claim 1, wherein the cross-linking agent is at least one selected from the group consisting of methyltributyloxidoxysilane, vinyltributylketoxime silane, propyltributylketoxime silane, phenyltributylketoxime silane, tetrabutylketoxime silane, methyltriacetonoxime silane, vinyltriacetoxybutyloxidosilane.
6. The silicone sealant according to claim 1, wherein the coupling agent is selected from at least one of vinyltriethoxysilane, γ -aminopropyl triethoxysilane, γ -glycidoxypropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane, γ -methacryloxypropyl trimethoxysilane, vinyltrimethoxysilane oligomer, vinyltriethoxysilane, oligomer of γ -aminopropyl triethoxysilane, and γ -aminopropyl trimethoxysilane.
7. The silicone sealant according to claim 1, wherein the catalyst is selected from at least one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate.
8. The method for preparing the silicone sealant according to any one of claims 1 to 7, comprising the steps of: uniformly mixing and stirring the alpha, omega-dihydroxyl polydimethylsiloxane, the dimethyl silicone oil, the branched silicone oil and the filler in parts by weight, stirring and dehydrating for 100-300min at 110-130 ℃ under the vacuum degree of 0.08-0.1 MPa, and cooling to obtain a base material; and then adding the base material into a planetary stirring kettle, adding a cross-linking agent, a coupling agent and a catalyst, and reacting for 30-80min under the vacuum degree of 0.06-0.1 MPa and the rotating speed of 200-800rpm to obtain the silicone sealant.
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| CN202111243251.9A CN114085641B (en) | 2021-10-25 | 2021-10-25 | Silicone sealant and preparation method thereof |
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| CN202111243251.9A CN114085641B (en) | 2021-10-25 | 2021-10-25 | Silicone sealant and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371638A (en) * | 2014-11-14 | 2015-02-25 | 浙江中天氟硅材料有限公司 | One-component ketoxime removal type sealant and preparation method thereof |
| CN107805392A (en) * | 2017-11-06 | 2018-03-16 | 苏州创励新材料科技有限公司 | One kind improves permeability one-component high heat conduction compound interface material and preparation method |
| CN109652007A (en) * | 2018-12-06 | 2019-04-19 | 成都硅宝科技股份有限公司 | Impervious oily bi-component silicone sealant of one kind and preparation method thereof |
| CN110982482A (en) * | 2019-12-25 | 2020-04-10 | 广西华纳新材料科技有限公司 | Low-modulus high-elongation silicone sealant with good adhesion and preparation method thereof |
-
2021
- 2021-10-25 CN CN202111243251.9A patent/CN114085641B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371638A (en) * | 2014-11-14 | 2015-02-25 | 浙江中天氟硅材料有限公司 | One-component ketoxime removal type sealant and preparation method thereof |
| CN107805392A (en) * | 2017-11-06 | 2018-03-16 | 苏州创励新材料科技有限公司 | One kind improves permeability one-component high heat conduction compound interface material and preparation method |
| CN109652007A (en) * | 2018-12-06 | 2019-04-19 | 成都硅宝科技股份有限公司 | Impervious oily bi-component silicone sealant of one kind and preparation method thereof |
| CN110982482A (en) * | 2019-12-25 | 2020-04-10 | 广西华纳新材料科技有限公司 | Low-modulus high-elongation silicone sealant with good adhesion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张玉龙等."常用热固性塑料及其成型技术".浙江科学技术出版社,2004,(第1版),第317-318页. * |
| 黄文润."热硫化硅橡胶".四川科学技术出版社,2009,(第1版),第81-82页. * |
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