A kind of organic silicon sealant for wind turbine assembly
By preparing the combination of phenol resin containing phosphorus silicon and materials such as α,ω-dihydroxypolysiloxane, the problem of insufficient bonding and flame retardant properties of silicone sealants is solved, and high hardness, strength and resistance are achieved The improvement of combustion performance is suitable for wind turbines and other fields.
Patent Information
- Application Number
- CN202411311366.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-20
- Publication Date
- 2024-12-27
- Estimated Expiration
- 2044-09-20
AI Technical Summary
Traditional silicone sealants have shortcomings in their bonding performance and flame retardant properties, and cannot meet the needs of special areas such as fire resistance and flame retardant.
By preparing a combination of phenol resin containing phosphorus silicon and α,ω-dihydroxypolysiloxane and other materials, a crosslinking agent, tackifier and catalyst are added to form a high-performance silicone sealant to improve its hardness and pull Extension and shear strength and flame retardant properties.
It significantly improves the hardness and bonding properties of the sealant, and gives it high flame retardant properties, can form a stable carbon layer structure at high temperatures, significantly improves the limit oxygen index and vertical combustion performance, and is suitable for wind turbines and other fields.
Smart Images
Figure CN118834657B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic silicon sealants, in particular to an organic silicon sealant used for assembling a wind turbine generator set. Background Art
[0002] Silicone sealants have good weather resistance, aging resistance, waterproof and other properties, and are widely used in road traffic, wind turbine equipment, solar cells, building facilities and other fields. Traditional silicone sealants have low strength, poor bonding performance, and are not flame retardant, and cannot meet the actual application in special fields such as fire retardancy.
[0003] Phenolic resin is a high-performance polymer material with excellent strength, bonding and flame retardant properties. It has good practical applications in adhesives, coatings, silicone rubber and other materials. For example, the paper "Preparation and Performance Research of Boron Phenolic / Silicone Rubber-based Ablation-Resistant Thermal Insulation Materials" reported the use of white carbon black, boron phenolic resin and other raw materials to improve the ablation resistance, crack strength and other properties of silicone rubber materials. Introducing organic boron, organic silicon, phosphate and other groups into phenolic resin can give phenolic resin functional effects such as flame retardancy, expanding the practical application of phenolic resin in sealants and other aspects. Summary of the invention
[0004] The invention solves the problems of poor bonding performance and poor flame retardant performance of organic silicon sealant.
[0005] Technical solution: A silicone sealant, comprising the following steps:
[0006] Step A: Add phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde solution into a flask, stir and heat to 55-65°C, add sodium hydroxide, react for 2-3h, then add phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde solution, heat to 80-90°C, continue to react for 3-4h, dehydrate by reduced pressure distillation, and dry to obtain silicon-phosphorus-containing phenolic resin.
[0007] Step B: Add α,ω-dihydroxy polysiloxane, silicon-phosphorus phenolic resin, filler, crosslinking agent, tackifier, and catalyst into a planetary mixer, stir and mix, and discharge to obtain an organosilicon sealant.
[0008] Furthermore, in step A, the molar ratio of phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde is (80-95):(5-20):(140-170).
[0009] Furthermore, in step B, the mass of the silicon-phosphorus phenolic resin is 5-30% of the mass of the α,ω-dihydroxy polysiloxane.
[0010] Furthermore, in step B, the filler is calcium carbonate or fumed silica.
[0011] Furthermore, in step B, the crosslinking agent is methyl tributylidene oxime silane, the tackifier is 3-aminopropyltriethoxysilane, and the catalyst is dibutyltin dilaurate.
[0012] Furthermore, the preparation method of the silicon-phosphorus-containing phenol monomer comprises the following steps:
[0013] Step (1): add ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and p-hydroxybenzaldehyde to a flask, heat to 40-55°C, react for 8-12 hours, then cool to room temperature, add sodium borohydride, wherein the molar ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, p-hydroxybenzaldehyde, and sodium borohydride is 100:(200-220):(240-260); react for 3-4 hours, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry with anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate.
[0014] Step (2): Add ethanol, the intermediate and 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide in a molar ratio of 100:(240-300) to a flask, heat to 60-70°C, react for 12-18 hours, add water to dilute after the reaction, add dichloromethane to extract, collect the organic phase, dry with anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized with ethanol to obtain a silicon-phosphorus-containing phenol monomer.
[0015] Furthermore, silicone sealants are used in the assembly of wind turbines.
[0016] The technical effect is: the present invention uses 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, p-hydroxybenzaldehyde, and 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide as raw materials to prepare a new type of phosphorus-silicon-containing silicon-phosphorus-phenol monomer, and then polymerizes it with phenol and formaldehyde to obtain a silicon-phosphorus-phenol-formaldehyde resin.
[0017] The present invention uses α,ω-dihydroxy polysiloxane as the main adhesive of the silicone sealant, silicon-phosphorus-containing phenolic resin as a modifier, and adds methyl tributylidene oxime silane as a crosslinking agent, 3-aminopropyl triethoxysilane as a tackifier, dibutyltin dilaurate as a catalyst, fillers and other auxiliary agents to obtain the silicone sealant. The molecular chain of the silicon-phosphorus-containing phenolic resin contains the same siloxane structural unit as the α,ω-dihydroxy polysiloxane, which significantly improves the compatibility between the phenolic resin and the silicone sealant. The phenolic resin has good mechanical strength and bonding properties, and is added to the silicone sealant to significantly improve the hardness and tensile shear strength of the sealant.
[0018] The phenolic resin of the present invention has high carbonization and flame retardancy, and at the same time introduces a phosphate flame retardant group, generates substances such as phosphoric acid during combustion, promotes the dehydration of the phenolic resin and the sealant matrix into carbon, forms a stable carbon layer structure, has the effects of heat insulation, oxygen isolation, smoke suppression, etc., thereby improving the limiting oxygen index and vertical combustion performance of the sealant, and has good flame retardancy. It has good practical applications in the fields of high-performance sealants, wind turbine assembly, etc. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 It is a reaction formula for preparing silicon-phosphorus-containing phenol monomer.
[0020] Figure 2 It is the reaction formula for preparing silicon-phosphorus phenolic resin. DETAILED DESCRIPTION
[0021] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.
[0022] The mass fraction of the formaldehyde solution of the present invention is 37%. The CAS number of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 2469-55-8, and the CAS number of p-hydroxybenzaldehyde is 123-08-0. The CAS number of 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide is 61481-13-8. Example 1
[0023] (1): Add 15 mL of ethanol, 4 mmol of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and 8.8 mmol of p-hydroxybenzaldehyde to a flask, heat to 40°C, react for 10 h, then cool to room temperature, add 10 mmol of sodium borohydride, react for 3 h, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry over anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate.
[0024] (2): Add 40 mL of ethanol, 5 mmol of the intermediate, and 12 mmol of 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide into a flask, heat to 70°C, and react for 12 hours. After the reaction, add water to dilute, add dichloromethane to extract, collect the organic phase, dry it with anhydrous sodium sulfate, filter it, and distill it under reduced pressure. The product is recrystallized from ethanol to obtain a silicon-phosphorus-containing phenol monomer.
[0025] (3): Add 40mmol of phenol, 6mmol of silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 65mmol of formaldehyde into a flask, stir and heat to 65°C, add 1.6mmol of sodium hydroxide, react for 2h, then add 47mmol of phenol, 7mmol of silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 90mmol of formaldehyde, heat to 90°C, continue to react for 4h, dehydrate by vacuum distillation, and dry to obtain a silicon-phosphorus-containing phenol-formaldehyde resin.
[0026] (4): Add 1 kg of α, ω-dihydroxypolysiloxane, 50 g of silicon-phosphorus phenolic resin, 120 g of calcium carbonate filler, 58 g of crosslinking agent methyl tributylidene silane, 22 g of tackifier 3-aminopropyltriethoxysilane, and 1 g of catalyst dibutyltin dilaurate into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant. Example 2
[0027] (1): Add 20 mL of ethanol, 4 mmol of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and 8 mmol of p-hydroxybenzaldehyde to a flask, heat to 55°C, react for 8 hours, then cool to room temperature, add 10.4 mmol of sodium borohydride, react for 4 hours, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry it with anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate.
[0028] (2): Add 30 mL of ethanol, 5 mmol of the intermediate, and 14 mmol of 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide into a flask, heat to 65°C, and react for 18 hours. After the reaction, add water to dilute, add dichloromethane to extract, collect the organic phase, dry it with anhydrous sodium sulfate, filter it, and distill it under reduced pressure. The product is recrystallized from ethanol to obtain a silicon-phosphorus-containing phenol monomer.
[0029] (3): Add 35 mmol phenol, 10 mmol silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 60 mmol formaldehyde into a flask, stir and heat to 65°C, add 1.2 mmol sodium hydroxide, react for 2 h, then add 45 mmol phenol, 10 mmol silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 80 mmol formaldehyde, heat to 80°C, continue to react for 4 h, dehydrate by vacuum distillation, and dry to obtain a silicon-phosphorus-containing phenol-formaldehyde resin.
[0030] (4): Add 1 kg of α, ω-dihydroxypolysiloxane, 50 g of silicon-phosphorus phenolic resin, 90 g of calcium carbonate filler, 66 g of crosslinking agent methyl tributylidene silane, 14 g of tackifier 3-aminopropyltriethoxysilane, and 1.2 g of catalyst dibutyltin dilaurate into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant. Example 3
[0031] (1): Add 20 mL of ethanol, 4 mmol of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and 8.8 mmol of p-hydroxybenzaldehyde to a flask, heat to 50°C, react for 12 hours, then cool to room temperature, add 9.6 mmol of sodium borohydride, react for 4 hours, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry it with anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate.
[0032] (2): Add 40 mL of ethanol, 5 mmol of the intermediate, and 15 mmol of 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide into a flask, heat to 60°C, and react for 18 hours. After the reaction, add water to dilute, add dichloromethane to extract, collect the organic phase, dry it with anhydrous sodium sulfate, filter it, and distill it under reduced pressure. The product is recrystallized from ethanol to obtain a silicon-phosphorus-containing phenol monomer.
[0033] (3): Add 45mmol phenol, 2mmol silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 75mmol formaldehyde into a flask, stir and heat to 55°C, add 1.4mmol sodium hydroxide, react for 3h, then add 50mmol phenol, 3mmol silicon-phosphorus-containing phenol monomer, and an aqueous solution containing 95mmol formaldehyde, heat to 85°C, continue to react for 4h, dehydrate by vacuum distillation, and dry to obtain a silicon-phosphorus-containing phenol-formaldehyde resin.
[0034] (4): Add 1 kg of α, ω-dihydroxypolysiloxane, 50 g of silicon-phosphorus phenolic resin, 70 g of filler fumed silica, 52 g of crosslinking agent methyl tributylidene oxime silane, 26 g of tackifier 3-aminopropyltriethoxysilane, and 1 g of catalyst dibutyltin dilaurate into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant. Example 4
[0035] The difference between this embodiment and embodiment 1 is that the amount of silicon-phosphorus phenolic resin used in the silicone sealant is 120 g, and the other steps are the same. Example 5
[0036] The difference between this embodiment and embodiment 1 is that the amount of silicon-phosphorus phenolic resin used in the silicone sealant is 200 g, and the other steps are the same. Example 6
[0037] The difference between this embodiment and embodiment 1 is that the amount of silicon-phosphorus phenolic resin used in the silicone sealant is 300 g, and the other steps are the same.
[0038] Comparative Example 1
[0039] The difference between this comparative example and Example 1 is that the amount of silicon-phosphorus-containing phenolic resin is 120 g and no silicon-phosphorus-containing phenolic resin is added to the silicone sealant, and the other steps are the same.
[0040] (1): Add 1 kg of α,ω-dihydroxypolysiloxane, 120 g of calcium carbonate filler, 58 g of methyltributylidene oxime silane crosslinker, 22 g of 3-aminopropyltriethoxysilane thickener, and 1 g of dibutyltin dilaurate catalyst into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant.
[0041] Comparative Example 2
[0042] The main difference between this comparative example and Example 1 is that no silicon-phosphorus-containing phenolic resin is added when preparing the phenolic resin.
[0043] (1): Add 45mmol of phenol and an aqueous solution containing 65mmol of formaldehyde to a flask, stir and heat to 65℃, add 1.6mmol of sodium hydroxide, react for 2h, then add 55mmol of phenol and an aqueous solution containing 90mmol of formaldehyde, heat to 90℃, continue to react for 4h, dehydrate by vacuum distillation, and dry to obtain phenolic resin.
[0044] (2): Add 1 kg α, ω-dihydroxypolysiloxane, 50 g phenolic resin, 120 g filler calcium carbonate, 58 g crosslinking agent methyl tributylidene silane, 22 g tackifier 3-aminopropyltriethoxysilane, and 1 g catalyst dibutyltin dilaurate into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant.
[0045] Comparative Example 3
[0046] The main difference between this comparative example and Example 1 is that when preparing the phenolic resin, the intermediate is used instead of the silicon-phosphorus-containing phenolic resin.
[0047] (1): Add 15 mL of ethanol, 4 mmol of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and 8.8 mmol of p-hydroxybenzaldehyde to a flask, heat to 40°C, react for 10 h, then cool to room temperature, add 10 mmol of sodium borohydride, react for 3 h, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry over anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate.
[0048] (2): Add 40mmol phenol, 6mmol intermediate, and an aqueous solution containing 65mmol formaldehyde into a flask, stir and heat to 65°C, add 1.6mmol sodium hydroxide, react for 2h, then add 47mmol phenol, 7mmol intermediate, and an aqueous solution containing 90mmol formaldehyde, heat to 90°C, continue to react for 4h, dehydrate by vacuum distillation, and dry to obtain a silicon-containing phenolic resin.
[0049] (3): Add 1 kg of α,ω-dihydroxypolysiloxane, 50 g of silicon-containing phenolic resin, 120 g of filler calcium carbonate, 58 g of crosslinking agent methyl tributylidene silane, 22 g of tackifier 3-aminopropyltriethoxysilane, and 1 g of catalyst dibutyltin dilaurate into a planetary mixer, stir and mix, and discharge to obtain a silicone sealant.
[0050] The silicone sealant was added into the mold and vulcanized at room temperature for 7 days to prepare a test specimen.
[0051] The combustion performance was tested according to GB / T 10707-2008. The hardness was tested according to GB / T 531.1-2008. The tensile shear strength was tested according to GB / T 13936-2014. The substrate was two aluminum alloy metal sheets. The test results are as follows.
[0052]
[0053] As can be seen from the above table, compared with Comparative Example 1, the limiting oxygen index of the silicone sealant of Examples 1-6 is significantly improved, and the vertical combustion level reaches FV-1 to FV-0 level, and the hardness and tensile shear strength are very good, showing excellent flame retardant properties, strength and bonding properties. This is because silicon-phosphorus phenolic resin is added to the silicone sealant of Examples 1-6, and the siloxane structural unit identical to α, ω-dihydroxy polysiloxane is introduced into the phenolic resin molecular chain, which significantly improves the compatibility between the phenolic resin and the silicone sealant. The phenolic resin has good mechanical strength and bonding properties. When added to the silicone sealant, the hardness and tensile shear strength of the sealant can be significantly improved. In addition, the phenolic resin has high carbonization and flame retardancy, and at the same time, the phosphate flame retardant group is introduced, and substances such as phosphoric acid are produced during combustion, which promotes the dehydration of the phenolic resin and the sealant matrix into carbon, forming a stable carbon layer structure, which has the effects of heat insulation, oxygen isolation, and smoke suppression, thereby improving the flame retardant properties of the sealant.
[0054] The phenolic resin in Comparative Example 2 does not have a siloxane structure and a phosphate flame retardant group. The compatibility between the phenolic resin and α,ω-dihydroxypolysiloxane is poor, and it is difficult to effectively improve the hardness and tensile shear strength of the sealant. Moreover, it does not contain a phosphate flame retardant group, and the phenolic resin has poor flame retardant properties for the sealant.
[0055] Comparative Example 3: When preparing the phenolic resin, an intermediate was added, and the obtained phenolic resin contained a siloxane structural unit, which had good compatibility with the silicone sealant and could significantly improve the hardness and tensile shear strength of the sealant. However, the phenolic resin did not contain a phosphate flame retardant group, and had poor flame retardant properties for the sealant.
[0056] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. A silicone sealant, characterized in that: The preparation method of the organic silicon sealant comprises the following steps: Step A: Add phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde solution into a flask, stir and heat to 55-65° C., add sodium hydroxide, react for 2-3 hours, then add phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde solution, heat to 80-90° C., continue to react for 3-4 hours, dehydrate by vacuum distillation, and dry to obtain silicon-phosphorus-containing phenolic resin; Step B: adding α,ω-dihydroxy polysiloxane, silicon-phosphorus phenolic resin, filler, crosslinking agent, tackifier, and catalyst into a planetary mixer, stirring and mixing, and discharging to obtain an organosilicon sealant; The preparation method of the silicon-phosphorus-containing phenol monomer comprises the following steps: Step (1): add ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and p-hydroxybenzaldehyde to a flask, heat to 40-55°C, react for 8-12 hours, then cool to room temperature, add sodium borohydride, react for 3-4 hours, add glacial acetic acid and water, adjust the pH to neutral, add dichloromethane for extraction, collect the organic phase, dry with anhydrous sodium sulfate, filter, and distill under reduced pressure. The product is recrystallized from dichloromethane to obtain an intermediate; Step (2): add ethanol, intermediate, 2,6,7-trioxa-1-phosphobicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide into a flask, add water to dilute after the reaction, add dichloromethane to extract, collect the organic phase, dry it with anhydrous sodium sulfate, filter it, distill it under reduced pressure, and recrystallize the product with ethanol to obtain a silicon-phosphorus-containing phenol monomer; In the step (1), the molar ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, p-hydroxybenzaldehyde, and sodium borohydride is 100:(200-220):(240-260); In the step (2), the molar ratio of the intermediate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-(chloromethyl)-1-oxide is 100:(240-300).
2. The organic silicon sealant according to claim 1, characterized in that: In the step A, the molar ratio of phenol, silicon-phosphorus-containing phenol monomer, and formaldehyde is (80-95): (5-20): (140-170).
3. The organic silicon sealant according to claim 1, characterized in that: In the step B, the mass of the silicon-phosphorus phenolic resin is 5-30% of the mass of the α,ω-dihydroxy polysiloxane.
4. The organic silicon sealant according to claim 1, characterized in that: In the step B, the filler is calcium carbonate or fumed silica.
5. The organic silicon sealant according to claim 1, characterized in that: In the step B, the crosslinking agent is methyl tributylidene oxime silane, the tackifier is 3-aminopropyltriethoxysilane, and the catalyst is dibutyltin dilaurate.
6. The organic silicon sealant according to claim 1, characterized in that: In the step (2), the reaction temperature is 60-70°C and the reaction time is 12-18h.
7. Use of the organic silicon sealant according to any one of claims 1 to 6 in the assembly of a wind turbine.