Antipollution adjuvants, methods of making and use

Abstract

The application discloses a kind of anti-pollution aids, preparation method and application.Amino silane coupling agent is slowly added to toluene solvent containing dehydrated castor oil, and reacted at 60-80 DEG C for 12-24 hours, and the oil product, i.e., the anti-pollution aid, is obtained after separation and purification.The novel anti-pollution aid prepared by the application is mainly used in silicone sealant products, has no easy migration, and can significantly improve the anti-pollution performance of sealant used outdoors.

Description

Technical Field

[0001] This invention relates to the field of silicone sealant technology, specifically to a method for preparing and applying a novel anti-fouling additive in silicone sealants for outdoor use. Background Technology

[0002] Silicone materials possess excellent weather resistance, aging resistance, superior high and low temperature resistance, electrical insulation properties, and adhesive properties, enabling long-term use in natural environments. They are widely used in building curtain walls, energy-saving doors and windows, and photovoltaic new energy fields. However, silicone sealants have drawbacks such as easy dust accumulation on the surface and easy migration of some components. During outdoor use, the sealant surface itself is easily contaminated by dust, and component migration can lead to contamination of surrounding substrates, even posing a risk of adhesive and sealant failure. Therefore, the silicone sealant application industry has placed higher demands on sealants, namely, the development of anti-contamination silicone sealants that do not easily accumulate dust on the surface and contain no easily migrating components.

[0003] Japanese patents JP62-1750 and JP62-7763 add drying oils to the formulation, which provides antifouling effects. However, because the drying oils are free in the sealant and have limited compatibility, they will slowly leach out during storage and outdoor use, affecting the sealant's shelf life and performance. US patents US4460740 and US4695603 describe adding surfactants to the adhesive to achieve antifouling effects, but this antifouling effect is short-lived and affects the sealant's adhesion. CN102627939 and CN100381535 both use hydrogen-containing silicone oil and drying oil adducts as antifouling components added to the adhesive. Although the antifouling effect is extended, the antifouling components are free in the sealant and are physically mixed, still posing a significant risk of migration and leaching.

[0004] With the continuous expansion of applications for silicone sealants, higher requirements are being placed on their performance. Therefore, it is urgent to develop anti-fouling sealants with good anti-fouling properties and minimal component migration. Summary of the Invention

[0005] The present invention aims to provide a method for preparing a non-migrating anti-fouling additive for use in silicone sealants, which can significantly improve the anti-fouling performance of silicone sealants.

[0006] In view of the problems of the prior art, the present invention provides a novel anti-pollution additive, the molecular structure of which is as follows:

[0007] ,

[0008] At least one of them is R.

[0009] , ,or One of them, where n=0 or 1; R1 is CH3 or (OR2); R2 is methyl or ethyl.

[0010] The aforementioned anti-fouling additive is used in silicone sealant products for outdoor use.

[0011] This invention also provides a method for preparing the above-mentioned novel anti-pollution additive, comprising the following steps:

[0012] (1) Add a certain amount of dehydrated castor oil to a flask containing toluene solvent;

[0013] (2) After heating the oil bath to 60 ℃~80 ℃, slowly add a certain amount of aminosilane coupling agent;

[0014] (3) After the addition is complete, maintain a constant temperature of 60 ℃~80 ℃ and stir for 12~24 h;

[0015] (4) Remove the toluene solvent by vacuum distillation to obtain the new anti-pollution additive.

[0016] In the above preparation step (1), the concentration range of dehydrated castor oil in the toluene solvent is 0.1–0.5 mol / L, wherein the molecular formula of dehydrated castor oil is:

[0017] .

[0018] In the above preparation step (2), the molar ratio of the amount of aminosilane coupling agent added to dehydrated castor oil is (1-6):1. The aminosilane coupling agent includes: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane.

[0019] This invention uses aminosilane coupling agent and dehydrated castor oil as raw materials to synthesize a series of novel anti-pollution additives containing silane coupling agent, and applies the anti-pollution additives of this invention to outdoor silicone sealants.

[0020] Compared with existing technologies, it has the following advantages:

[0021] (1) This novel anti-pollution additive is made from aminosilane coupling agent and dehydrated castor oil as raw materials. The synthesis process is simple and easy to prepare.

[0022] (2) This new anti-pollution additive has good compatibility with silicone sealant. Aminosilane coupling agent is a silicon-based material and belongs to the same series of products as silicone sealant. It can make the dehydrated castor oil modified by aminosilane coupling agent evenly distributed in the sealant, so that the sealant can obtain more uniform anti-pollution performance;

[0023] (3) This novel anti-fouling additive does not easily migrate within the sealant. The silane oxygen group of the aminosilane coupling agent can chemically react with the basic polymer in the adhesive. The anti-fouling additive is fixed in the silicone sealant through chemical bonds, making it more difficult for it to migrate out of the sealant, thereby giving the sealant better and more durable anti-fouling performance. Attached Figure Description

[0024] Figure 1 The molecular structure of the anti-pollution additive of the present invention is shown below, wherein:

[0025] Anti-pollution additive 1 prepared in Example 1: n=0, R1=CH3, R2=methyl;

[0026] Anti-pollution additive 2 prepared in Example 2: n=0, R1=CH3, R2=ethyl;

[0027] Anti-pollution additive 3 prepared in Example 3: n=0, R1=OR2, R2=methyl;

[0028] Anti-pollution additive 4 prepared in Example 4: n=0, R1=OR2, R2=ethyl;

[0029] Anti-pollution additive 5 prepared in Example 5: n=1, R1=CH3, R2=methyl;

[0030] Anti-pollution additive 6 prepared in Example 6: n=1, R1=CH3, R2=ethyl;

[0031] Anti-pollution additive 7 prepared in Example 7: n=1, R1=OR2, R2=methyl;

[0032] Anti-pollution additive 8 prepared in Example 8: n=1, R1=OR2, R2=ethyl;

[0033] Figure 2 The molecular structure of the anti-pollution additive of the present invention is shown below, wherein:

[0034] Anti-pollution additive 9 prepared in Example 9: R2 = methyl;

[0035] Anti-pollution additive 10 prepared in Example 10: R2 = ethyl;

[0036] Figure 3 The molecular structure of the anti-pollution additive of the present invention is shown below, wherein:

[0037] Anti-pollution additive 11 prepared in Example 11: R2 = methyl;

[0038] Anti-pollution additive 12 prepared in Example 12: R2 = ethyl. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0040] Example 1

[0041] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.02 mol of 3-aminopropylmethyldimethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 1.

[0042] Example 2

[0043] Add 0.06 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.12 mol of 3-aminopropylmethyldiethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 2.

[0044] Example 3

[0045] Add 0.10 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.30 mol of γ-aminopropyltrimethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 3.

[0046] Example 4

[0047] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.08 mol of γ-aminopropyltriethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 4.

[0048] Example 5

[0049] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and then slowly add 0.10 mol of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 5.

[0050] Example 6

[0051] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and then slowly add 0.12 mol of N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 6.

[0052] Example 7

[0053] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and then slowly add 0.06 mol of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. After the addition is complete, stir the reaction for 18 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 7.

[0054] Example 8

[0055] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and then slowly add 0.06 mol of N-β-(aminoethyl)-γ-aminopropyltriethoxysilane. After the addition is complete, stir the reaction for 24 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 8.

[0056] Example 9

[0057] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 60 °C and then slowly add 0.06 mol of N-n-butyl-3-aminopropyltrimethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 9.

[0058] Example 10

[0059] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 80 °C and then slowly add 0.06 mol of N-n-butyl-3-aminopropyltriethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 10.

[0060] Example 11

[0061] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.06 mol of γ-ureidopropyltrimethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 11.

[0062] Example 12

[0063] Add 0.02 mol of dehydrated castor oil to a flask containing 200 mL of toluene solvent. Heat the oil bath to 70 °C and slowly add 0.06 mol of γ-ureidopropyltriethoxysilane. After the addition is complete, stir the reaction for 12 h. Remove the toluene solvent by vacuum distillation to obtain anti-pollution additive 12.

[0064] Add approximately 4 wt% of the anti-fouling additives 1-12 prepared in Examples 1-12 to the silicone sealant formulation. Silicone sealant formulation (parts by weight):

[0065] 100 parts of α,ω-dihydroxypolysiloxane

[0066] 150 parts of nano calcium carbonate

[0067] 10 parts of dimethyl silicone oil (or the additives of this invention, dehydrated castor oil, or an adduct of hydrogen-containing silicone oil and dehydrated castor oil)

[0068] 10 parts crosslinking agent

[0069] 3 parts of silane coupling agent

[0070] 0.1 parts catalyst

[0071] The crosslinking agent is methyl tributanone oxime silane; the coupling agent is γ-aminopropyltriethoxy

[0072] Silane; the catalyst is dibutyltin dilaurate.

[0073] The application performance, mechanical properties, and contamination performance of silicone sealants before and after the addition of anti-fouling additives were tested according to GB / T 13477 test method. The contamination performance test method was to fill the sealant material between two porous substrates and cure it to form a sample. The surface contamination of the sealant was observed for a long time under normal conditions. After heat treatment and low temperature aging treatment, the experimental sample was evaluated. The changes on the substrate surface were visually observed, the maximum contamination width and thickness were measured, and the contamination phenomenon on the outer surface of the substrate and inside the body was recorded. The results are shown in Tables 1 and 2.

[0074] Table 1. Effect of adding the anti-fouling additive of this invention on the product performance of silicone sealant.

[0075]

[0076] Table 2. Effect of adding the anti-fouling additive of the present invention on the anti-fouling performance of organosilicon sealant.

[0077]

[0078] The results in Table 1 show that:

[0079] Control 1 was added with only dimethyl silicone oil; no other anti-fouling additives were added. Controls 2 and 3 were added with dehydrated castor oil, hydrogen-containing silicone oil and dehydrated castor oil adduct, respectively. Experiments 1 to 12 were added with anti-fouling additives 1 to 12 synthesized in the present invention in the examples.

[0080] Compared with Control 1, after adding dehydrated castor oil, the silicone sealant showed 20%, 30%, and 20% interface damage to the substrate's qualitative adhesion, qualitative adhesion after cold drawing and hot pressing, and qualitative adhesion after immersion in water, respectively. Other properties showed no significant differences.

[0081] Compared with Control 1, there was no significant difference in the performance of the silicone sealant after adding hydrogen-containing silicone oil and dehydrated castor oil adduct.

[0082] Compared with control 1, the tensile modulus of the silicone sealant was slightly increased after adding the anti-pollution additives 1-12 synthesized in this invention in experiments 1-12, while the other properties were not significantly different.

[0083] The results in Table 2 show that:

[0084] Control 1 was added with only dimethyl silicone oil; no other anti-fouling additives were added. Controls 2 and 3 were added with dehydrated castor oil, hydrogen-containing silicone oil and dehydrated castor oil adduct, respectively. Experiments 1 to 12 were added with anti-fouling additives 1 to 12 synthesized in the present invention in the examples.

[0085] Compared to Control 1, Controls 2 and 3 showed improved anti-fouling performance of the sealant surface after the addition of dehydrated castor oil, hydrogen-containing silicone oil, and dehydrated castor oil adducts in short-term follow-up (3–6 months). However, in long-term follow-up (9–12 months), varying degrees of surface contamination still appeared on the sealant surface. After heat aging and low-temperature aging, the substrate of Controls 2 and 3 was found to be severely contaminated compared to Control 1.

[0086] Compared with Control 1, in Experiments 1-12, after adding the anti-fouling additives 1-12 synthesized in this invention, no contamination was found on the surface of the sealant of the test specimens during long-term monitoring. In Control 1, severe contamination appeared on the surface of the sealant after 9 months of storage. After heat aging and low-temperature aging, neither Experiments 1-12 nor Control 1 showed any contamination of the substrate by the sealant.

[0087] In summary, the antifouling additive of the present invention makes reasonable use of the antifouling properties of dehydrated castor oil and locks it into the sealant through chemical incorporation, integrating it with the sealant. This prevents the migration of the additive from causing contamination of the sealant surface and substrate, and significantly improves the antifouling performance of silicone sealants used outdoors.

[0088] Although the invention has been described herein with reference to illustrative embodiments, it should be understood that many other modifications and implementations can be devised by those skilled in the art, which will fall within the scope and spirit of the principles disclosed herein. More specifically, various variations and modifications can be made to the components and / or layout of the subject matter combination within the scope of this disclosure. Besides variations and modifications to the components and / or layout, other uses will be apparent to those skilled in the art.

Claims

1. The application of anti-fouling additives in outdoor silicone sealant products, characterized in that, As an anti-pollution additive; the molecular structure of the anti-pollution additive is as follows: ， Where R is , ,or One of them, where n=0 or 1; R1 is CH3 or (OR2); R2 is methyl or ethyl.

2. The application of the anti-fouling additive according to claim 1 in outdoor silicone sealant products, characterized in that, The preparation method of the anti-pollution additive includes the following steps: (1) Add a certain amount of dehydrated castor oil to a flask containing toluene solvent; (2) After heating the oil bath to 60 ℃~80 ℃, add a certain amount of aminosilane coupling agent dropwise; (3) After the addition is complete, maintain a constant temperature of 60 ℃~80 ℃ and stir for 12~24 h; (4) Remove the toluene solvent by vacuum distillation to obtain the anti-pollution additive.

3. The application of the anti-fouling additive according to claim 2 in outdoor silicone sealant products, characterized in that, The concentration range of dehydrated castor oil in the toluene solvent is 0.1–0.5 mol / L, wherein the molecular formula of the dehydrated castor oil is: 。 4. The application of the anti-fouling additive according to claim 2 in outdoor silicone sealant products, characterized in that, The molar ratio of the aminosilane coupling agent added to the dehydrated castor oil is (1-6):

1.

5. The application of the anti-fouling additive according to claim 2 in outdoor silicone sealant products, characterized in that, The aminosilane coupling agent is selected from one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane.

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