A branched vinyl silicone oil composition, a method for producing the same, and an anti-fogging release agent
By preparing a branched vinyl silicone oil composition, controlling the acid value and impurity ion content, increasing the degree of branching, and forming a network structure, the atomization problem of the release agent in the high-speed coating process was solved, and the safety and coating effect were improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2025-01-02
- Publication Date
- 2026-05-19
AI Technical Summary
Existing release agents are prone to atomization during high-speed coating, leading to health hazards and equipment damage. Meanwhile, traditional inhibitors introduce impurities that affect the coating effect.
A branched vinyl silicone oil composition was prepared, comprising branched vinyl silicone oil and micro-crosslinkers. The acid value and impurity ion content were controlled. A network structure was formed through high branching degree and micro-crosslinkers, which reduced the generation of small molecules and improved adhesion to suppress atomization.
It significantly reduces atomization during high-speed coating, improves the safety of the coating process and the life of the equipment, while maintaining the peel strength of the release agent.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organosilicon materials, specifically to a branched vinyl silicone oil composition and its preparation method, and an anti-fogging release agent. Background Technology
[0002] With the increasing demand for release agents, increasing coating speed has become an important means for related companies to reduce costs and increase efficiency. A few years ago, a coating speed of 200m / min might have been considered the industry standard; however, with the improvement of the domestic solvent-free coating machinery manufacturing level, the operating speed of new equipment can now generally reach 300-500m / min, and the world's fastest coating line speed can even reach 1100m / min.
[0003] The "atomization" phenomenon during high-speed coating has limited the industry's development and has become an urgent problem to be solved. The mechanism of "atomization" during high-speed coating is mainly due to the centrifugal force generated by the rotation of the coating head, which "throws out" some small-molecule silicone oil from the release agent, thus forming mist. This mist not only poses a health hazard to operators but also accumulates on the coating machine and workshop floor, causing production safety accidents and shortening the lifespan of the coating machine.
[0004] CN115785452A discloses an anti-fogging additive for release agent coating and its preparation method. The anti-fogging additive includes at least grafts of hydrogen-containing silicone oil and vinyl silicone oil, wherein the vinyl silicone oil includes at least branched vinyl silicone oil; furthermore, the branched vinyl silicone oil is end-capped with trialkoxysilane groups, and the hydrogen-containing silicone oil is end-capped with trialkoxysilane groups. When applied to release agents, the anti-fogging additive provided by this technical solution has a significant effect on suppressing fogging; however, excessively high or low overall viscosity can have a certain impact on the peel strength of the release agent.
[0005] Currently, the industry often uses the addition of inhibitors to suppress or weaken the atomization phenomenon of release agents during high-speed coating. However, this approach inevitably introduces new impurities, affecting the application performance or coating effect of the release agent. Therefore, how to prepare a low-atomization vinyl silicone oil for release agents has become an urgent technical problem to be solved in the industry. Summary of the Invention
[0006] To address the shortcomings of existing technologies, one of the objectives of this invention is to provide a branched vinyl silicone oil composition and its preparation method. The branched vinyl silicone oil composition contains branched vinyl silicone oil and a small amount of micro-crosslinkers, and features ultra-low acid value, low impurity ion content, and high stability.
[0007] A second objective of this invention is to provide an anti-fogging release agent comprising the above-mentioned branched vinyl silicone oil composition.
[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0009] In a first aspect, the present invention provides a branched vinyl silicone oil composition comprising a branched vinyl silicone oil having the structure shown in Formula I:
[0010] (R 1 (R 2 2SiO) n R 2 2SiO 1 / 2 ) a (SiO2) b (Ⅰ);
[0011] In the formula, R 1 For vinyl, R 2 It is methyl;
[0012] The value of a is an even number selected from 4 to 10, and the value of b is (a-2) / 2;
[0013] n is an integer selected from 10 to 200, preferably an integer from 20 to 200.
[0014] Specifically, in the structure shown in Formula I, the value of a can be 1, 5, 6, 7, 8, 9, 10, etc., the value of b can be 1, 2, 3, 4, etc., and n can be selected from 10, 30, 50, 70, 100, 120, 150, 180, 200, etc.
[0015] In one embodiment, the component with b=2-4 in the branched vinyl silicone oil having the structure shown in Formula I accounts for 12-30 wt%, for example 12 wt%, 15 wt%, 18 wt%, 20 wt%, 23 wt%, 25 wt%, 28 wt%, 30 wt%, etc., preferably 18-30%.
[0016] In one embodiment, the branched vinyl silicone oil composition, in addition to the branched vinyl silicone oil having the structure shown in Formula I, further includes 0.01-0.1 wt% of a micro-crosslinker, such as 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.06 wt%, 0.08 wt%, 0.1 wt%, etc., wherein the micro-crosslinker has the structure shown in Formula II:
[0017] (R 1 (R 2 2SiO) n R 2 2SiO) c (SiO2) d (II);
[0018] In the formula, R1 For vinyl, R 2 It is methyl;
[0019] The value of c is an even number selected from 6 to 12, and the value of d is an integer selected from 3 to 6;
[0020] n is an integer selected from 10 to 200.
[0021] Specifically, in the structure shown in Formula II, the value of c can be 6, 7, 8, 9, 10, 11, 12, etc., and the value of d can be 3, 4, 5, 6, etc.; n can be selected from 10, 30, 50, 70, 100, 120, 150, 180, 200, etc.
[0022] In one embodiment, the branched vinyl silicone oil composition has an acid value ≤0.001 mg KOH / g.
[0023] In one embodiment, the branched vinyl silicone oil composition has an impurity ion content of ≤10ppm;
[0024] The heteroions include potassium, sodium, sulfonate, etc. These ions mainly originate from acidic catalysts, alkaline neutralizers, and filter aids introduced during the preparation process. The presence of these ions will affect the neutralization effect and the storage stability of the product to a certain extent, and will also have a negative impact on the application effect and the equipment used in downstream industries.
[0025] Secondly, the present invention provides a method for preparing the above-mentioned branched vinyl silicone oil composition, comprising the following steps:
[0026] 1) A portion of the silicate ester is mixed with acid catalyst A and deionized water A to carry out a hydrolysis reaction, and then a vinyl end-capping agent is added to carry out a hydrolysis-condensation reaction with the remaining silicate ester, acid catalyst B and deionized water B.
[0027] 2) The reaction solution in step 1) is distilled to remove light components, then acidic auxiliaries are added for aging reaction, and then alkaline solution is added to adjust the pH to 5-7. After washing with water, branched siloxane small molecules are obtained.
[0028] 3) The branched siloxane small molecules from step 2) are mixed with siloxane cyclic molecules and acidic catalyst to carry out a ring-opening equilibrium reaction, and then a neutralizing agent is added to carry out a neutralization reaction. After filtration, the branched vinyl silicone oil composition is obtained.
[0029] In one embodiment, the silicate ester in step 1) is selected from one or two of methyl orthosilicate and ethyl orthosilicate, preferably ethyl orthosilicate; the silicate esters added in the two steps may be the same or different.
[0030] The acid catalyst A and acid catalyst B are selected from one or more of sulfuric acid, trifluoromethanesulfonic acid, and hydrochloric acid, with trifluoromethanesulfonic acid being preferred; the acid catalyst A and acid catalyst B may be the same or different.
[0031] The vinyl end-capping agent is selected from one or more of tetramethyldivinyldisiloxane and vinyl-terminated silicone oil, preferably tetramethyldivinyldisiloxane.
[0032] In one embodiment, the molar ratio of the end-capping agent to the total silicate in step 1) is 1.5-2:1, such as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc., preferably 1.7-1.8:1;
[0033] The silicate ester comprises 0.5-5% of the total silicate ester mass;
[0034] The amount of acid catalyst A is 0.02-2% of the mass of the partial silicate ester, for example, 0.02%, 0.05%, 0.1%, 0.3%, 0.5%, 0.7%, 1.0%, 1.2%, 1.5%, 1.8%, 2%, etc.; the mass of acid catalyst B is 0.05-0.2% of the sum of the mass of the vinyl end-capping agent and the remaining silicate ester, for example, 0.05%, 0.08%, 0.1%, 0.13%, 0.15%, 0.17%, 0.2%, etc.
[0035] The amount of deionized water A added is 40-60% of the molar amount of silicate ester, such as 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, etc.; the amount of deionized water B added is 2.5-4 times the molar amount of the remaining silicate ester, such as 2.5 times, 3 times, 3.5 times, 4 times, etc., preferably 2.5-3 times.
[0036] In one embodiment, the hydrolysis reaction in step 1) is carried out at a temperature of 30-50°C, such as 30°C, 32°C, 35°C, 37°C, 40°C, 42°C, 45°C, 48°C, 50°C, etc., and for a time of 0.05-0.5h, such as 0.05h, 0.1h, 0.15h, 0.2h, 0.25h, 0.3h, 0.35h, 0.4h, 0.45h, 0.5h, etc.
[0037] The hydrolysis-condensation reaction is carried out at a temperature of 70-85℃, such as 70℃, 72℃, 75℃, 77℃, 80℃, 82℃, 85℃, etc., preferably 78-85℃, for a time of 3-6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, etc., preferably 4-5h;
[0038] Specifically, during the reaction process, the deionized water A and B are gradually added to the reaction system, for example, by continuous, batch, or dropwise addition, with no particular requirement for the addition time;
[0039] Preferably, the deionized water B is added dropwise, with the addition temperature at 30-85℃, such as 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 85℃, etc., preferably 60-80℃, and the addition time at 0.1-1h, such as 0.1h, 0.2h, 0.4h, 0.6h, 0.8h, 1h, etc., preferably 0.2-0.5h. The addition is followed by a heat preservation reaction, meaning the addition time is not included in the above-mentioned reaction time.
[0040] In one embodiment, the acidic auxiliary agent in step 2) is selected from one or more of sulfuric acid, acetic acid, and propionic acid, preferably acetic acid;
[0041] Preferably, the amount of acidic additive added is 2-20% of the total mass of the capping agent and the remaining silicate ester in step 1);
[0042] The alkaline solution is selected from one or more of sodium carbonate solution and sodium bicarbonate solution, preferably sodium carbonate solution;
[0043] Preferably, the alkaline solution is an aqueous solution of alkali with a concentration of 4-6 wt%.
[0044] In one embodiment, the reaction solution in step 2) is distilled to remove light components. The distillation is carried out at a temperature of 100-140°C for 2-4 hours, preferably 2-3 hours.
[0045] Preferably, after removing the light components, the ethanol content in the system is less than 0.5 wt%; the light components removed by distillation mainly include deionized water, ethanol, and end-capping monomers.
[0046] In one embodiment, the aging reaction in step 2) is carried out at a temperature of 80-140°C, such as 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, etc., preferably 80-100°C, and for a reaction time of 2-6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc., preferably 3-4 hours.
[0047] After the aging reaction in step 2) of this invention is completed, the process also includes adding alkali solution to adjust the pH and washing with water. These are all conventional operations in the field and are not specifically limited by this invention. For example, washing with deionized water 2-6 times (preferably 3-4 times).
[0048] The branched siloxane small molecule obtained in step 2) of this invention has the structure shown in Formula III:
[0049] (R 1 R2 2SiO 1 / 2 ) a (SiO2) b (III);
[0050] In the formula, R 1 For vinyl, R 2 It is methyl;
[0051] The value of a is an even number selected from 4 to 10, and the value of b is (a-2) / 2;
[0052] For example, when a is 4 and b is 1, the specific structure of the branched siloxane small molecule shown in Formula III above is as follows:
[0053]
[0054] Furthermore, the branched siloxane small molecule obtained in step 2) also has the structure shown in formula IV:
[0055] (R 1 R 2 2SiO) c (SiO2) d (Ⅳ)
[0056] In the formula, R 1 For vinyl, R 2 It is methyl;
[0057] The value of c is an even number selected from 6 to 12, and the value of d is an integer selected from 3 to 6.
[0058] In one embodiment, the siloxane cyclic body in step 3) is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dimethylsiloxane mixed cyclic bodies, preferably octamethylcyclotetrasiloxane;
[0059] The acidic catalyst is selected from one or more of sulfonic acid resin, trifluoromethanesulfonic acid, and sulfuric acid, with trifluoromethanesulfonic acid being preferred;
[0060] The neutralizing agent is selected from one or more of calcium carbonate, sodium bicarbonate, and sodium carbonate, preferably calcium carbonate.
[0061] In one embodiment, the molar ratio of the branched siloxane small molecule to the siloxane ring in step 3) is 1:20-60, for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, etc.
[0062] The amount of acidic catalyst added is 0.01-0.3 wt%, for example, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, etc., based on the total mass of the system;
[0063] The neutralizing agent is added in an amount of 0.2-2 wt%, such as 0.2 wt%, 0.5 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, etc., preferably 5-10 wt%, based on the total mass of the system.
[0064] In one embodiment, the ring-opening equilibrium reaction in step 3) is carried out at a temperature of 30-70°C, such as 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, etc., and for a reaction time of 4-8 hours, such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, etc.
[0065] The neutralization reaction is carried out at a temperature of 10-40℃, such as 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, etc., preferably 30-40℃, and for a reaction time of 0.5-4h, such as 0.5h, 1h, 2h, 3h, 4h, preferably 2-3h.
[0066] In one implementation, the filtration described in step 3) can be carried out with the assistance of a filter aid. After filtration, post-processing operations such as deashing can be included. All of these can be carried out using conventional methods in the field and there are no special requirements.
[0067] Preferably, the filter aid is diatomaceous earth, and more preferably, two types of diatomaceous earth with different particle sizes are used as the filter aid. The mass ratio of the two types of diatomaceous earth with different particle sizes is preferably 0.8-1.2:1. The specific particle sizes of the two types of diatomaceous earth are not limited and can be selected from the conventional particle size range used in the field. For example, one specific operation method is to select two types of diatomaceous earth with preferably one large and one small particle size. First, the large particle size diatomaceous earth is mixed in, and after mixing for 0.5 hours, the small particle size diatomaceous earth is mixed in. After mixing evenly, the mixture is then subjected to pressure filtration. In addition, the diatomaceous earth must be added to the system after the neutralization process is completed to avoid unneutralized acid being adsorbed by the diatomaceous earth and squeezed out during the subsequent pressure filtration process, leaving residues in the system.
[0068] The operations described in the preparation method of this invention can be carried out in a protective gas environment, such as nitrogen.
[0069] Thirdly, the present invention also provides the use of the above-mentioned branched vinyl silicone oil composition in the preparation of release agents.
[0070] An anti-fogging release agent comprising the branched vinyl silicone oil composition of the present invention, specifically prepared from raw materials comprising the following parts by weight:
[0071] 100 parts of branched vinyl silicone oil composition,
[0072] 3-4 parts of hydrogen-containing silicone oil;
[0073] Platinum catalyst 0.5-4 parts.
[0074] The specific type of hydrogen-containing silicone oil is not limited, and can be selected from 20 viscosity high hydrogen-containing silicone oil (hydrogen content 1.6%), 30 viscosity high hydrogen-containing silicone oil (hydrogen content 1.6%), etc., with 20 viscosity high hydrogen-containing silicone oil being preferred.
[0075] The platinum catalyst is a conventional selection in the field, and there are no special requirements for it in this invention. For example, it can be selected from isopropanol-based cassette catalyst (Pt-5000), xylene-based cassette catalyst (Pt-5000), etc., with isopropanol-based cassette catalyst (Pt-5000) being preferred.
[0076] After mixing the above components according to the specified ratio, a slurry is obtained, which is the anti-fogging release agent. When using it, the slurry is applied quickly using a roller (gradually increasing the coating speed).
[0077] The anti-fogging release agent provided by this invention comprises the above-mentioned branched vinyl silicone oil composition. Its anti-fogging effect is analyzed and mainly achieved through two aspects:
[0078] 1) By controlling the acid value and impurity ion content in the branched vinyl silicone oil composition within a certain range, the side reactions of silicone oil products during reaction and storage can be weakened, especially the degradation reaction that may occur during long-term storage, thereby reducing the content of small molecules in the silicone oil system, fundamentally reducing the number of small molecules that cause atomization, and weakening the probability and degree of atomization during coating.
[0079] 2) The branched vinyl silicone oil composition has a high degree of silicone oil branching, that is, the polymer content in the branched siloxane small molecules is specifically increased (the content of b≥2 in the branched vinyl silicone oil mixture, and a small amount of micro crosslinkers), thereby improving the adhesion of silicone oil. After grafting reaction with hydrogen-containing silicone oil, a silicone oil morphology with a network-like structure is obtained, which plays a protective net role in the release agent coating process, to a certain extent increasing the difficulty of small silicone oil molecules being thrown out, thereby weakening the atomization phenomenon in the coating process.
[0080] Compared with modern technology, the advantages of this invention are as follows:
[0081] In this invention, by reducing the acid value and impurity ion content in the silicone oil product and increasing the degree of branching of the silicone oil, the branched vinyl silicone oil is used to prepare a release agent, which has a significant anti-fogging effect during high-speed coating. Detailed Implementation
[0082] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0083] Unless otherwise specified, the reagents, materials and instruments used in the following examples are all conventional reagents, materials and instruments in the art, and can be obtained commercially.
[0084] The sources of the main raw materials used in the various embodiments and comparative examples of this invention are as follows:
[0085]
[0086]
[0087] The main analytical methods used in the embodiments and comparative examples of this invention are as follows:
[0088] Acid value content test method: Chemical titration method is used to test the acid value content of the sample. For details, please refer to the acid value determination method shown in HG / T2366-2015.
[0089] Impurity ion testing method: Inductively coupled plasma mass spectrometry is used to determine the ion content;
[0090] Small molecule category determination method: Nuclear magnetic resonance analysis is used to characterize the category and structure of each component in the sample;
[0091] Volatile matter test method: high temperature difference method (150℃, 3g, 3h), that is, weigh 3g of sample and put it into a container with a specific mass of mg, dry it at 150℃ for 3h, and then measure the mass of the sample and the container again. The volatile matter calculation formula is (3+mn) / 3*100%, which is used to characterize the content of light components in the sample.
[0092] Sample aging test: Seal 100g of sample and store it in a 50℃ oven for aging test for 3 months;
[0093] Anti-fogging performance test: In a clean environment, an aerosol detector is used to measure whether aerosols are detected at a certain linear velocity to determine its anti-fogging performance.
[0094] Example 1
[0095] A method for preparing a branched vinyl silicone oil, comprising the following specific steps:
[0096] 1) Under a nitrogen atmosphere, 2.2 g (0.01056 mol) of tetraethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and heated to 35 °C for 5 min for hydrolysis reaction;
[0097] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of tetraethyl orthosilicate, and 0.29 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 70 °C, and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system over a period of 0.2 h. The mixture was then subjected to a hydrolysis-condensation reaction at 80 °C for 4 h.
[0098] 2) The light components were removed by distillation at 120℃ for 3 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.5wt%.
[0099] Then add 18g of acetic acid, age at 90℃ for 4h, then add 5wt% sodium bicarbonate solution to adjust the pH to 6, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation three times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0100] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2, c value is 8, and d value is 4.
[0101] The NMR characterization results are as follows: 1 HNMR (400MHz, CDCl3) δ0.15 (6H, s), δ5.18 (1H, d, J = 15.9Hz), δ5.31 (1H, m), δ5.42 (1H, dt, J = 15.8HZ, 6.2Hz).
[0102] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 970 g (3.27 mol) of octamethylcyclotetrasiloxane were added to a four-necked flask. Then, 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 50 °C for a ring-opening equilibrium reaction for 5 h. Then, 1 wt% of calcium carbonate was added to the system, and the neutralization reaction was carried out at 30 °C for 2 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1:1) were added sequentially and mixed for 0.5 h. After filtration and removal of light components, the branched vinyl silicone oil composition was obtained.
[0103] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 20 wt% where b = 2; wherein,
[0104] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.95 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2; n is 24-44;
[0105] The content of the micro-crosslinked body shown in Formula II is 0.05 wt%: In Formula II, R 1 For vinyl, R 2 It is a methyl group; the c value is 8, the d value is 4; and the n value is 24-44.
[0106] Example 2
[0107] This embodiment provides a method for preparing branched vinyl silicone oil, the specific steps of which are as follows:
[0108] 1) Under a nitrogen atmosphere, 2.2 g (0.0106 mol) of tetraethyl orthosilicate was mixed with 0.001 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and the mixture was heated to 40 °C for 20 min to hydrolyze the mixture.
[0109] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 78.91 g (0.5184 mol) of methyl orthosilicate, and 0.38 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 75 °C, and 28 g (1.5556 mol) of deionized water was slowly added dropwise to the above system over a period of 0.3 h. The mixture was then subjected to a hydrolysis-condensation reaction at 82 °C for 5 h.
[0110] 2) The light components were removed by distillation at 120℃ for 4 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.4wt%.
[0111] Then add 22.2g of propionic acid, age at 110℃ for 2h, then add 5wt% sodium bicarbonate solution to adjust the pH to 7, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation four times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0112] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-8, b value is 1-3, c value is 8-10, and d value is 4-5.
[0113] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 700 g (2.3599 mol) of octamethylcyclotetrasiloxane were added to a four-necked flask. Then, 0.02 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 70 °C for a ring-opening equilibrium reaction for 8 h. Next, 0.3 wt% of 2 g of calcium carbonate was added to the system, and the neutralization reaction was carried out at 20 °C for 4 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 0.8:1) were added sequentially and mixed for 0.5 h. The mixture was filtered and light-weighted to obtain a branched vinyl silicone oil composition.
[0114] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 25 wt% where b = 2-3; wherein,
[0115] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.97 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-8, b value is 1-3; n is 14-34;
[0116] The content of the micro-crosslinked body shown in Formula II is 0.03 wt%: In Formula II, R 1 For vinyl, R 2 It is a methyl group; the c value is 8-10, the d value is 4-5, and the n value is 14-34.
[0117] Example 3
[0118] This embodiment provides a method for preparing branched vinyl silicone oil, the specific steps of which are as follows:
[0119] 1) Under a nitrogen atmosphere, 1.1 g (0.0053 mol) of tetraethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.05 g (0.0028 mol) of deionized water, and the mixture was heated to 35 °C for 5 min to hydrolyze the mixture.
[0120] Then, 190 g (1.0193 mol) of tetramethyldivinyldisiloxane, 109.1 g (0.5237 mol) of tetraethyl orthosilicate, and 0.29 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 70 °C, and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system over a period of 0.2 h. The mixture was then subjected to a hydrolysis-condensation reaction at 80 °C for 4 h.
[0121] 2) The light components were removed by distillation at 120℃ for 3 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.5wt%.
[0122] Then add 18g of acetic acid, age at 90℃ for 4h, then add 5wt% sodium carbonate solution to adjust the pH to 6, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation three times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0123] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2, c value is 8, and d value is 4.
[0124] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 1300 g (4.3827 mol) of dimethylsiloxane mixed cyclic compounds were added to a four-necked flask. Then, 0.19 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 35 °C for ring-opening equilibrium reaction for 4 h. Then, 1.5 wt% of calcium carbonate was added to the system, and the neutralization reaction was carried out at 35 °C for 3 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1.2:1) were added sequentially and mixed for 0.5 h. After filtration and removal of light components, the branched vinyl silicone oil composition was obtained.
[0125] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 21 wt% where b = 2; wherein,
[0126] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.97 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2; n is 35-55;
[0127] The content of the micro-crosslinked body shown in Formula II is 0.03 wt%: In Formula II, R 1 For vinyl, R 2 It is a methyl group; the c value is 8, the d value is 4; and the n value is 35-55.
[0128] Example 4
[0129] This embodiment provides a method for preparing branched vinyl silicone oil, the specific steps of which are as follows:
[0130] 1) Under a nitrogen atmosphere, 2.2 g (0.0106 mol) of tetraethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and heated to 40 °C for 10 min for hydrolysis reaction;
[0131] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of tetraethyl orthosilicate, and 0.29 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 70 °C, and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system over a period of 0.4 h. After that, the hydrolysis-condensation reaction was carried out at 85 °C for 2 h.
[0132] 2) The light components were removed by distillation at 100℃ for 4 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.5wt%.
[0133] Then add 6g of acetic acid, age at 140℃ for 6h, then add 6wt% sodium bicarbonate solution to adjust the pH to 7, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation three times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0134] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2, c value is 8, and d value is 4.
[0135] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 1600 g (5.3941 mol) of dimethylsiloxane mixed cyclic compounds were added to a four-necked flask. Then, 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 65 °C for ring-opening equilibrium reaction for 6 h. Next, 16 g of calcium carbonate (1 wt% of calcium carbonate) was added to the system, and the neutralization reaction was carried out at 40 °C for 4 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1:1) were added sequentially and mixed for 0.5 h. After filtration and removal of light components, the branched vinyl silicone oil composition was obtained.
[0136] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 18 wt% where b = 2; wherein,
[0137] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.93 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2; n is 46-66;
[0138] The content of the micro-crosslinked body shown in Formula II is 0.07 wt%: In Formula II, R 1 For vinyl, R 2It is a methyl group; the c value is 8, the d value is 4; and the n value is 46-66.
[0139] Example 5
[0140] This embodiment provides a method for preparing branched vinyl silicone oil, the specific steps of which are as follows:
[0141] 1) Under a nitrogen atmosphere, 4.4 g (0.0211 mol) of tetraethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.2 g (0.0111 mol) of deionized water, and heated to 35 °C for 5 min for hydrolysis reaction;
[0142] Then, 160 g (0.8584 mol) of tetramethyldivinyldisiloxane, 105.8 g (0.5078 mol) of tetraethyl orthosilicate, and 0.29 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 70 °C, and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system over a period of 0.2 h. The mixture was then subjected to a hydrolysis-condensation reaction at 80 °C for 4 h.
[0143] 2) The light components were removed by distillation at 120℃ for 3 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.5wt%.
[0144] Then add 18g of acetic acid, age at 90℃ for 4h, then add 5wt% sodium carbonate solution to adjust the pH to 6, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation three times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0145] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-8, b value is 1-3, c value is 6-10, and d value is 3-5.
[0146] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 970 g (3.2702 mol) of dimethylsiloxane mixed cyclic compounds were added to a four-necked flask. Then, 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 55 °C for a ring-opening equilibrium reaction for 7 h. Next, 1 wt% of calcium carbonate was added to the system, and the reaction was carried out at 30 °C for 1 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1:1) were added sequentially and mixed for 0.5 h. The mixture was filtered and light-weighted to obtain a branched vinyl silicone oil composition.
[0147] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 28 wt% where b = 2-3; wherein,
[0148] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.91 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-8, b value is 1-3; n is 24-44;
[0149] The content of the micro-crosslinked body shown in Formula II is 0.09 wt%: In Formula II, R 1 For vinyl, R 2 It is a methyl group; the c value is 6-10, the d value is 3-5; and the n value is 24-44.
[0150] Example 6
[0151] This embodiment provides a method for preparing branched vinyl silicone oil, the specific steps of which are as follows:
[0152] 1) Under a nitrogen atmosphere, 2.2 g (0.0106 mol) of tetraethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and the mixture was heated to 30 °C for 25 min to hydrolyze the mixture.
[0153] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of tetraethyl orthosilicate, and 0.29 g of trifluoromethanesulfonic acid were added and mixed thoroughly. The mixture was heated to 70 °C, and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system over a period of 0.3 h. The mixture was then subjected to a hydrolysis-condensation reaction at 78 °C for 6 h.
[0154] 2) The light components were removed by distillation at 140℃ for 2 hours until the light components stopped flowing out. At this time, the content of light components in the system was reduced to below 0.5wt%.
[0155] Then add 50g of acetic acid, age at 80℃ for 2h, then add 4wt% sodium carbonate solution to adjust the pH to 6, let stand, separate into layers, and remove the lower aqueous phase; add 30g of deionized water, mix for 0.5h, let stand, separate into layers, and remove the lower aqueous phase. Repeat this operation three times; then, remove the acidic light components by high-temperature distillation (120℃, 4h) to obtain branched siloxane small molecules;
[0156] Branched siloxane small molecules include the structures shown in formulas III and IV, where R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2, c value is 8, and d value is 4.
[0157] 3) Under a nitrogen atmosphere, 30 g (a mixture, totaling approximately 0.096 mol) of branched siloxane small molecules and 970 g (3.2702 mol) of dimethylsiloxane mixed cyclic compounds were added to a four-necked flask. Then, 1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 55 °C for a ring-opening equilibrium reaction for 7 h. Next, 2 wt% of sodium carbonate was added to the system, and the neutralization reaction was carried out at 40 °C for 4 h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1:1) were added sequentially and mixed for 0.5 h. After filtration and removal of light components, the branched vinyl silicone oil composition was obtained.
[0158] This branched vinyl silicone oil composition, having the structure shown in Formula I, has a component content of 16 wt% where b = 2; wherein,
[0159] The branched vinyl silicone oil with the structure shown in Formula I has a content of 99.95 wt%: In Formula I, R 1 For vinyl, R 2 It is a methyl group; a value is 4-6, b value is 1-2; n is 24-44;
[0160] The content of the micro-crosslinked body shown in Formula II is 0.05 wt%: In Formula II, R 1 For vinyl, R 2 It is a methyl group; the c value is 8, the d value is 4; and the n value is 24-44.
[0161] Comparative Example 1
[0162] Linear vinyl silicone oil was prepared according to the method in Example 5, except that branched siloxane small molecules were not synthesized. Under the condition of maintaining the same vinyl content, tetramethyldivinyldisiloxane was directly used as the end-capping agent. The specific steps are as follows: 1) Under a nitrogen atmosphere, 35.8g (0.1921mol) of tetramethyldivinyldisiloxane and 970g (3.2702mol) of dimethylsiloxane were added to a four-necked flask. Then, 0.1wt% of trifluoromethanesulfonic acid was added to the system, mixed, and heated to 55°C for ring-opening equilibrium reaction for 7h. Then, 1wt% of calcium carbonate was added to the system, and neutralization reaction was carried out at 30°C for 1h. Then, two types of diatomaceous earth (DZ1000 and 545RVS, with a mass ratio of 1:1) were added in sequence and mixed for 0.5h. After filtration and removal of light content, the linear vinyl silicone oil composition was obtained.
[0163] The linear vinyl silicone oil composition has the following structure:
[0164] R 1 R 2 2SiO(R) 2 2SiO) n Si R2 2 R 1 ;
[0165] In the formula, R 1 For vinyl, R 2 It is a methyl group; n is 58-78;
[0166] The compositions prepared in Examples 1-6 and Comparative Example 1 were subjected to parameter testing, and the test data results are shown in Table 1 below:
[0167] Table 1
[0168]
[0169] Application Examples 1-6
[0170] Prepare an anti-fogging release agent according to the following formula:
[0171] 100 parts of branched vinyl silicone oil composition
[0172] 3.2 parts of hydrogen-containing silicone oil (purchased from Dow Corning, MHX-1107)
[0173] 1 part platinum catalyst (isopropanol system, Pt-5000ppm);
[0174] The branched vinyl silicone oil compositions used in Examples 1-6 were adopted sequentially.
[0175] The above raw materials were mixed according to the formula to obtain a mixed slurry. Then, the slurry was used as a release agent and rapidly coated using a roller (gradually increasing the coating speed). At the same time, the conditions for the appearance of aerosols in the surrounding environment were recorded. The results are shown in Table 2.
[0176] Application Comparative Example 1
[0177] The formulations of Application Examples 1-6 above were followed, except that the branched vinyl silicone oil compositions were replaced sequentially with the vinyl silicone oil compositions prepared in Comparative Example 1, while other operations and conditions remained unchanged. The results are shown in Table 2.
[0178] Table 2 Performance test data for examples and comparative examples
[0179]
[0180]
[0181] As can be seen from the above data, the branched vinyl silicone oil composition provided by the present invention has high stability and exhibits significant anti-fogging properties when applied as a release agent.
[0182] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.
Claims
1. A branched vinyl silicone oil composition, characterized in that, Including branched vinyl silicone oils having the structure shown in Formula I: (R 1 (R 2 2SiO) n R 2 2SiO 1 / 2 ) a (SiO2) b (Ⅰ); In the formula, R 1 For vinyl, R 2 It is methyl; The value of a is an even number selected from 4 to 10, and the value of b is (a-2) / 2; n is an integer selected from 10 to 200; The branched vinyl silicone oil composition includes 0.01-0.1 wt% of micro-crosslinkers; The branched vinyl silicone oil composition has an acid value ≤0.001 mg KOH / g; The branched vinyl silicone oil composition has an impurity ion content of ≤10ppm.
2. The branched vinyl silicone oil composition according to claim 1, characterized in that, In the branched vinyl silicone oil with the structure shown in Formula I, the proportion of the component with b=2-4 is 12-30wt%.
3. The branched vinyl silicone oil composition according to claim 2, characterized in that, When b=2-4, the component proportion is 18-30%.
4. The branched vinyl silicone oil composition according to claim 1, characterized in that, The micro-crosslinked body has the structure shown in Formula II: (R 1 (R 2 2SiO) n R 2 2SiO 1 / 2 ) c (SiO2) d (Ⅱ); In the formula, R 1 For vinyl, R 2 It is methyl; The value of c is an even number selected from 6 to 12, and the value of d is an integer selected from 3 to 6; n is an integer selected from 10 to 200.
5. A method for preparing the branched vinyl silicone oil composition according to any one of claims 1-4, characterized in that, Includes the following steps: 1) A portion of the silicate ester is mixed with acid catalyst A and deionized water A to carry out a hydrolysis reaction, and then a vinyl end-capping agent is added to carry out a hydrolysis-condensation reaction with the remaining silicate ester, acid catalyst B and deionized water B; 2) The reaction solution in step 1) is distilled to remove light components, then acidic auxiliaries are added for aging reaction, and then alkaline solution is added to adjust the pH to 5-7. After washing with water, branched siloxane small molecules are obtained. 3) The branched siloxane small molecules from step 2) are mixed with siloxane cyclic molecules and acidic catalyst to carry out a ring-opening equilibrium reaction, and then a neutralizing agent is added to carry out a neutralization reaction. After filtration, the branched vinyl silicone oil composition is obtained. Step 1) The acid catalyst A and acid catalyst B are selected from one or more of sulfuric acid, trifluoromethanesulfonic acid, and hydrochloric acid.
6. The method for preparing the branched vinyl silicone oil composition according to claim 5, characterized in that, Step 1) The silicate ester is selected from one or both of methyl orthosilicate and ethyl orthosilicate; The vinyl end-capping agent is selected from one or more of tetramethyldivinyldisiloxane and vinyl-terminated silicone oil; Step 1) The molar ratio of the end-capping agent to the total silicate is 1.5-2:1; The silicate ester constitutes 0.5-5% of the total silicate ester mass; The amount of acid catalyst A is 0.02-2% of the mass of the partial silicate ester; the mass of acid catalyst B is 0.05-0.2% of the sum of the mass of the vinyl end-capping agent and the remaining silicate ester. The amount of deionized water A added is 40-60% of the molar amount of the silicate ester; the amount of deionized water B added is 2.5-4 times the molar amount of the remaining silicate ester.
7. The method for preparing the branched vinyl silicone oil composition according to claim 6, characterized in that, The molar ratio of the end-capping agent to the total silicate is 1.7-1.8:
1.
8. The method for preparing the branched vinyl silicone oil composition according to claim 6, characterized in that, The amount of deionized water B added is 2.5-3 times the molar amount of the remaining silicate ester.
9. The method for preparing the branched vinyl silicone oil composition according to claim 5, characterized in that, The hydrolysis reaction described in step 1) is carried out at a temperature of 30-50℃ for a time of 0.05-0.5h. The hydrolysis-condensation reaction described in step 1) is carried out at a temperature of 70-85℃ for 3-6 hours. In step 1), deionized water A and B are gradually added to the reaction system.
10. The method for preparing the branched vinyl silicone oil composition according to claim 9, characterized in that, The hydrolysis-condensation reaction is carried out at a temperature of 78-85℃ for 4-5 hours.
11. The method for preparing the branched vinyl silicone oil composition according to claim 9, characterized in that, The deionized water B is added by drip feeding at a temperature of 30-85℃ for 0.1-1 hours.
12. The method for preparing the branched vinyl silicone oil composition according to claim 11, characterized in that, The feeding temperature is 60-80℃, and the feeding time is 0.2-0.5h.
13. The method for preparing the branched vinyl silicone oil composition according to claim 5, characterized in that, Step 2) The acidic auxiliaries are selected from one or more of sulfuric acid, acetic acid, and propionic acid; Step 2) The amount of acidic additive added is 2-20% of the total mass of the capping agent and remaining silicate ester in Step 1); Step 2) The alkaline solution is selected from one or more of sodium carbonate solution and sodium bicarbonate solution; the alkaline solution is an aqueous solution of alkali with a concentration of 4-6 wt%. Step 2) The reaction solution is distilled to remove light components. The distillation is carried out at a temperature of 100-140℃ for 2-4 hours. The aging reaction described in step 2) is carried out at a temperature of 80-140℃ for 2-6 hours.
14. The method for preparing the branched vinyl silicone oil composition according to claim 13, characterized in that, The distillation process takes 2-3 hours.
15. The method for preparing the branched vinyl silicone oil composition according to claim 13, characterized in that, The aging reaction is carried out at a temperature of 80-100℃ for 3-4 hours.
16. The method for preparing the branched vinyl silicone oil composition according to claim 5, characterized in that, Step 3) The siloxane cyclic body is selected from one or more of the following: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dimethylsiloxane mixed cyclic bodies; The acidic catalyst is selected from one or more of sulfonic acid resin, trifluoromethanesulfonic acid, and sulfuric acid; The neutralizing agent is selected from one or more of calcium carbonate, sodium bicarbonate, and sodium carbonate. Step 3) The molar ratio of the branched siloxane small molecule to the siloxane ring is 1:20-60; The amount of acidic catalyst added is 0.01-0.3 wt%, based on the total mass of the system; The amount of neutralizing agent added is 0.2-2 wt%, based on the total mass of the system.
17. The method for preparing the branched vinyl silicone oil composition according to claim 16, characterized in that, The amount of neutralizing agent added is 5-10 wt%, based on the total mass of the system.
18. The method for preparing the branched vinyl silicone oil composition according to claim 5, characterized in that, The ring-opening equilibrium reaction described in step 3) is carried out at a temperature of 30-70℃ for 4-8 hours. The neutralization reaction described in step 3) is carried out at a temperature of 10-40℃ for a time of 0.5-4 hours. The filtration described in step 3) is carried out with the assistance of a filter aid.
19. The method for preparing the branched vinyl silicone oil composition according to claim 18, characterized in that, The neutralization reaction is carried out at a temperature of 30-40℃ for 2-3 hours.
20. The method for preparing the branched vinyl silicone oil composition according to claim 18, characterized in that, The filter aid is diatomaceous earth.
21. The method for preparing the branched vinyl silicone oil composition according to claim 18, characterized in that, The filter aid consists of two types of diatomaceous earth with different particle sizes.
22. An anti-fogging release agent, characterized in that, The composition includes the branched vinyl silicone oil composition according to any one of claims 1-4 or the branched vinyl silicone oil composition prepared by the method according to any one of claims 5-21, specifically, it is obtained from raw materials comprising the following parts by weight: 100 parts of branched vinyl silicone oil composition, 3-4 parts of hydrogen-containing silicone oil; Platinum catalyst 0.5-4 parts.