Oil-filled transparent ketoxime thixotropic silicone sealant and its manufacturing method

Abstract

The present invention relates to the technical field of sealants, and in particular to an oil-filled transparent ketoxime thixotropic silicone sealant and a method for manufacturing the same, wherein the silicone sealant uses a medium-viscosity α,ω-dihydroxy polysiloxane as a base polymer, and an interaction force can be formed by adding a thickener to the base polymer and white carbon black in the sealant system to improve the rheology of the sealant system, thereby obtaining an oil-filled transparent ketoxime thixotropic silicone sealant and a method for manufacturing the same. The sealant belongs to a single-component condensation type room temperature vulcanized silicone rubber, which is composed of α,ω-dihydroxy polysiloxane, a plasticizer, a crosslinking agent, a filler, resveratrol, a coupling agent, a catalyst and a thickener, and the method for manufacturing the same is simple and feasible.

Description

Technical Field

[0001] The invention relates to the technical field of sealants, and in particular to an oil-filled transparent ketoxime thixotropic silicone sealant and a preparation method thereof. Background Art

[0002] Silicone sealants are widely used in construction, electronic appliances, automobiles, lighting, machinery, new energy and artificial organs due to their excellent high and low temperature resistance, excellent UV resistance and weather aging resistance, good hydrophobicity, good air permeability and physiological inertness. Single-component condensation-type room temperature vulcanized silicone sealants are widely used in the construction industry in the fields of door and window bonding and sealing, building exterior wall materials bonding and sealing, sun roof bonding and sealing, as well as caulking, bonding and sealing of indoor materials.

[0003] Regarding the construction properties of sealants, sealants are required to have good extrusion properties and good thixotropy, both of which not only ensure the construction efficiency of sealants, but also ensure the construction quality of sealants. It is well known that the proportion of plasticizers in sealants will affect the extrusion properties and thixotropy of sealants. Generally speaking, the greater the proportion of plasticizers, the better the sealant extrusion properties, but the worse the sealant thixotropy; conversely, the sealant extrusion properties are good, but the sealant thixotropy will become worse. Similarly, the viscosity of α,ω-dihydroxypolysiloxane in sealants will also affect the extrusion properties and thixotropy of sealants. Generally, the greater the viscosity of α,ω-dihydroxypolysiloxane, the worse the extrusion properties and the better the thixotropy.

[0004] Therefore, the present invention uses a simple and feasible manufacturing method to find a suitable thickener. Under the conditions of using medium-viscosity α, ω-dihydroxy polysiloxane and / or increasing the proportion of plasticizer, the thickener is used to treat white carbon black in situ to improve the rheological properties of the sealant system, thereby solving the extrusion and thixotropy problems of the sealant system without increasing or even reducing the manufacturing cost of the sealant. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide an oil-filled transparent ketoxime thixotropic silicone sealant and a method for manufacturing the same, so as to solve the problems of extrusion and thixotropy of the sealant system.

[0006] Based on the above purpose, the present invention provides an oil-filled transparent ketoxime thixotropic silicone sealant, comprising the following components in parts by weight: 100 parts of α, ω-dihydroxy polysiloxane, 80-150 parts of a plasticizer, 15-30 parts of a cross-linking agent, 15-30 parts of a filler, 1-5 parts of resveratrol, 0-3 parts of a coupling agent, 1-5 parts of a thickener, and 0.1-0.5 parts of a catalyst.

[0007] Preferably, the α,ω-dihydroxy polysiloxane is one of α,ω-dihydroxy polydimethylsiloxane, α,ω-dihydroxy polydiethylsiloxane and α,ω-dihydroxy polymethylphenylsiloxane, and has a viscosity of 20000 mPa.s-100000 mPa.s (25°C).

[0008] Preferably, the plasticizer is one of industrial white oil and trimethyl-terminated polydimethylsiloxane, the industrial white oil has a distillation range of 210-360°C and a density (20°C) of 780-830kg / m3, and the methyl-terminated polydimethylsiloxane has a viscosity of 50-500mPs.a (25°C).

[0009] Preferably, the industrial white oil is one of No. 3 white oil and No. 5 white oil.

[0010] Preferably, the crosslinking agent is one or more of methyltributylacetoximosilane, vinyltributylacetoximosilane, tetrabutylketoximesilane, phenyltributylacetoximosilane, tetramethylisobutylketoximesilane, and vinyltri(methylisobutylketoxime)silane.

[0011] Preferably, the filler has a specific surface area of ​​140-170m 2 / g of hydrophilic fumed silica and a specific surface area of ​​20-100m 2 / g of precipitated silica.

[0012] Preferably, the coupling agent is one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxytrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0013] Preferably, the thickener is one or more of monoethanolamine borate, diethanolamine diborate, and diethanolamine monoborate.

[0014] Preferably, the catalyst is one of dibutyltin dilaurate, dibutyltin diacetate, and dimethyltin dicaneodecanoate.

[0015] The present invention also provides a method for preparing an oil-filled transparent ketoxime thixotropic silicone sealant, comprising the following steps:

[0016] (1) Preparation of pre-treated material: Add the cross-linking agent into the reactor, turn on the cooling water and nitrogen protection, and stir at 200-500 rpm, then add the thickener dropwise within 10-60 minutes. When the temperature of the reactor drops to room temperature, filter the material, and the filtrate after filtration is the pre-treated material.

[0017] (2) Preparation of sealant: α, ω-dihydroxy polysiloxane, plasticizer and pretreatment material are added into a reactor, stirred at 300-500 rpm under a vacuum degree of 0.09-0.098 MPa, and reacted for 20-50 min. Then, white carbon black and resveratrol are added, and stirring is continued for 20-50 min under the same vacuum degree and stirring rate. Finally, coupling agent and catalyst are added, and stirring is continued for 20-50 min under the same vacuum degree and stirring rate to obtain an oil-filled transparent ketoxime thixotropic silicone sealant.

[0018] Beneficial effects of the present invention:

[0019] The present invention skillfully introduces ethanolamine borate and resveratrol into the formula of silicone sealant. After the ethanolamine borate is hydrolyzed, it is cross-linked in the main network of the silicone sealant under the action of a catalyst. After the resveratrol is added, the nitrogen of the ethanolamine borate and the phenolic hydroxyl group in the resveratrol can form hydrogen bonds with the surface hydroxyl group of white carbon black, thereby changing the rheological properties of the sealant system.

[0020] The core additives in the present invention are ethanolamine borate and resveratrol. Ethanolamine borate is widely used as an emulsifier, cutting fluid additive, etc., with low toxicity and stable performance. Resveratrol is widely present in at least 72 plants of 21 families and 31 genera such as Vitis, Polygonum, Arachis, Veratrum, etc., with abundant sources and is environmentally friendly. DETAILED DESCRIPTION

[0021] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0022] Example 1

[0023] (1) Preparation of pretreatment material: 21 g of methyl tributylidene silane was added to a reactor, cooling water and nitrogen protection were turned on, and stirring was performed at 300 rpm. Then, 1 g of monoethanolamine borate was added dropwise within 20 min. When the temperature of the reactor dropped to room temperature, the material was filtered out, and the filtrate after filtration was the pretreatment material.

[0024] (2) Preparation of sealant: 100 g of α,ω-dihydroxy polydimethylsiloxane with a viscosity of 80,000 mPa.s, 120 g of No. 3 white oil and 22 g of pre-treated material were added to a reactor, stirred at 400 rpm under a vacuum of 0.096 MPa, reacted for 25 min, and then 22 g of a 150 m2 carbonyl ether with a specific surface area of ​​150 m2 was added. 2 / g of hydrophilic fumed silica and 1g of resveratrol were added, and stirring was continued for 25 minutes at the same vacuum degree and stirring rate. Finally, 0.3g of dibutyltin dilaurate was added, and stirring was continued for 25 minutes at the same vacuum degree and stirring rate to obtain an oil-filled transparent ketoxime thixotropic silicone sealant.

[0025] Example 2

[0026] (1) Preparation of pre-treated material: The amount of monoethanolamine borate added was changed to 1.75 g, and the rest was the same as in Example 1.

[0027] (2) Preparation of sealant: The amount of pre-treated material added was changed to 22.75 g, the content of resveratrol was changed to 1.75 g, and the rest was the same as in Example 1.

[0028] Example 3

[0029] (1) Preparation of pre-treated material: The amount of monoethanolamine borate added was changed to 3.5 g, and the rest was the same as in Example 1.

[0030] (2) Preparation of sealant: The amount of pre-treated material added was changed to 24.5 g, the content of resveratrol was changed to 3.5 g, and the rest was the same as in Example 1.

[0031] Example 4

[0032] (1) Preparation of pretreated material: The amount of monoethanolamine borate added was changed to 5 g, and the rest was the same as in Example 1.

[0033] (2) Production of sealant: The amount of pre-treated material added was changed to 26 g, the content of resveratrol was changed to 5 g, and the rest was the same as in Example 1.

[0034] Example 5

[0035] (1) Preparation of pretreatment material: 21 g of methyl tributylidene silane was added to a reactor, cooling water and nitrogen protection were turned on, and stirring was performed at 300 rpm. Then, 1.75 g of diethanolamine monoborate was added dropwise within 20 min. When the temperature of the reactor dropped to room temperature, the material was filtered out, and the filtrate after filtration was the pretreatment material.

[0036] (2) Preparation of sealant: 100 g of α,ω-dihydroxy polydimethylsiloxane with a viscosity of 80,000 mPa.s, 120 g of No. 3 mineral oil and 22.75 g of pre-treated material were added to a reactor, stirred at 400 rpm under a vacuum of 0.096 MPa, reacted for 25 min, and then 22 g of a 150 m 2 / g of hydrophilic fumed silica was added, and stirring was continued for 25 minutes at the same vacuum degree and stirring rate. Finally, 0.3g of dibutyltin dilaurate and 1.75g ​​of resveratrol were added, and stirring was continued for 25 minutes at the same vacuum degree and stirring rate to obtain an oil-filled transparent ketoxime thixotropic silicone sealant.

[0037] Example 6

[0038] (1) Preparation of pre-treated material: The amount of monoethanolamine borate added was changed to 1.75 g, and the rest was the same as in Example 1.

[0039] (2) Preparation of sealant: 100 g of α,ω-dihydroxy polydimethylsiloxane with a viscosity of 80,000 mPa.s, 120 g of No. 3 mineral oil and 22.75 g of pre-treated material were added to a reactor, stirred at 400 rpm under a vacuum of 0.096 MPa, reacted for 25 min, and then 22 g of a 150 m 2 / g of hydrophilic fumed silica and 1.75g ​​of resveratrol were added, and stirring was continued for 25min at the same vacuum degree and stirring rate. Finally, 1.2g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 1g of γ-glycidoxytrimethoxysilane and 0.3g of dibutyltin dilaurate were added, and stirring was continued for 25min at the same vacuum degree and stirring rate to obtain an oil-filled transparent ketoxime thixotropic silicone sealant.

[0040] Comparative Example 1

[0041] (1) Preparation of pre-treated material: The amount of monoethanolamine borate added was changed to 0, and the rest was the same as in Example 2.

[0042] (2) Preparation of sealant: The amount of pre-treated material added was changed to 21 g, the amount of resveratrol added was changed to 0, and the rest was the same as in Example 2.

[0043] Comparative Example 2

[0044] (1) Preparation of pretreated material: The addition amount of monoethanolamine borate was changed to 7, and the rest was the same as in Example 2.

[0045] (2) Preparation of sealant: The amount of pre-treated material added was changed to 28 g, and the rest was the same as in Example 2.

[0046] Comparative Example 3

[0047] (1) Preparation of pre-treated material: same as in Example 2.

[0048] (2) Preparation of sealant: The amount of resveratrol added was changed to 0, and the rest was the same as in Example 2.

[0049] Comparative Example 4

[0050] (1) Preparation of pre-treated material: The amount of monoethanolamine borate added was changed to 0, and the rest was the same as in Example 2.

[0051] (2) Preparation of sealant: The amount of pre-treated material added was changed to 21 g, and the rest was the same as in Example 2.

[0052] Performance Test:

[0053] The surface drying time of sealant shall be in accordance with GB / T 13477.5-2002, Method B;

[0054] The sealant consistency is in accordance with GB 1749-1979;

[0055] Thixotropy test of sealant: vertically, under the same conditions, apply sealant on a vertically placed glass plate, mark the lower end of the sealant, and record the distance from the lower end of the sealant after 30 minutes. horizontally, under the same conditions, apply sealant on a horizontally placed glass plate and make a circle, measure the diameter of the sealant circle, and record whether the diameter of the sealant circle changes after 30 minutes. If the diameter does not change, it is called non-deformation, otherwise, it is called deformation;

[0056] The surface drying time of the sealant after aging for 24 hours at 90°C shall comply with GB / T 13477.5-2002, method B.

[0057] Table 1 Performance test results of Examples 1-6

[0058]

[0059] Table 2 Performance test results of Example 2 and Comparative Examples 1-4

[0060]

[0061] Data analysis: From Examples 1-6, it can be seen that the silicone sealant prepared by the formula and manufacturing method of the present invention has excellent rheological properties, not only the consistency is significantly reduced, but also the fluidity in the horizontal and vertical directions is significantly weakened, and its thixotropy is significantly enhanced. From Examples 1-6 and Comparisons 2 and 4, it can be seen that ethanolamine borate and resveratrol have a significant synergistic effect. From Example 2 and Comparison 1, it can be seen that the surface drying time and aging surface drying time of the sealant added with ethanolamine borate are significantly reduced, which is because the amine group in the borate shortens the surface drying time of the sealant.

[0062] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention (including the claims) is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0063] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An oil-filled transparent ketoxime thixotropic silicone sealant, characterized in that: The invention comprises the following components in parts by weight: 100 parts of α, ω-dihydroxy polysiloxane, 80-150 parts of plasticizer, 15-30 parts of crosslinking agent, 15-30 parts of filler, 1-5 parts of resveratrol, 0-3 parts of coupling agent, 1-5 parts of thickener and 0.1-0.5 parts of catalyst; The filler has a specific surface area of ​​140-170m 2 / g of hydrophilic fumed silica and a specific surface area of ​​20-100m 2 / g of precipitated silica; The thickener is one or more of monoethanolamine borate, diethanolamine diborate and diethanolamine monoborate.

2. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 1, characterized in that: The α,ω-dihydroxy polysiloxane is one of α,ω-dihydroxy polydimethylsiloxane, α,ω-dihydroxy polydiethylsiloxane and α,ω-dihydroxy polymethylphenylsiloxane, and has a viscosity of 20000 mPa.s-100000 mPa.s at 25°C.

3. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 1, characterized in that: The plasticizer is industrial white oil and trimethyl end-capped polydimethylsiloxane. The distillation range of the industrial white oil is 210-360°C, and the density at 20°C is 780-830kg / m 3 The viscosity of the trimethyl-terminated polydimethylsiloxane at 25° C. is 50-500 mPa.s.

4. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 3, characterized in that: The industrial white oil is one of No. 3 white oil and No. 5 white oil.

5. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 1, characterized in that: The crosslinking agent is one or more of methyltributylacetoximosilane, vinyltributylacetoximosilane, tetrabutylketoximesilane, phenyltributylacetoximosilane, tetramethylisobutylketoximesilane and vinyltri(methylisobutylketoxime)silane.

6. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 1, characterized in that: The coupling agent is one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxytrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.

7. The oil-filled transparent ketoxime thixotropic silicone sealant according to claim 1, characterized in that: The catalyst is one of dibutyltin dilaurate, dibutyltin diacetate and dimethyltin diceneodecanoate.

8. A method for producing the oil-extended transparent ketoxime thixotropic silicone sealant according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Preparation of pre-treated material: add the cross-linking agent into the reactor, turn on the cooling water and nitrogen protection, and stir at 200-500 rpm, then add the thickener dropwise within 10-60 min, and when the temperature of the reactor drops to room temperature, filter the material, and the filtrate after filtration is the pre-treated material; (2) Preparation of sealant: α,ω-dihydroxypolydimethylsiloxane, plasticizer and pretreatment material are added into a reactor, stirred at 300-500 rpm under a vacuum degree of 0.09-0.098 MPa, and reacted for 20-50 min. Then, white carbon black and resveratrol are added, and stirred for 20-50 min under the same vacuum degree and stirring rate. Finally, coupling agent and catalyst are added, and stirred for 20-50 min under the same vacuum degree and stirring rate to obtain an oil-filled transparent ketoxime thixotropic silicone sealant.

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