Branched chain vinyl silicone oil composition, preparation method thereof and anti-fogging release agent

Abstract

The invention provides a branched chain vinyl silicone oil composition, a preparation method thereof and an anti-fogging release agent. The branched chain vinyl silicone oil composition comprises branched chain vinyl silicone oil with a structure as shown in the following formula I: (R1 (R22SiO) nR22SiO1 / 2) a (SiO2) b (I), in the formula, R1 is vinyl, and R2 is methyl; a is an even number selected from 4-10, and b is (a-2) / 2; and n is an integer selected from 10 to 200, preferably an integer from 20 to 200. The branched chain vinyl silicone oil has the characteristics of ultralow acid value, low impurity ion content, high stability, micro-crosslinking and the like; the branched chain vinyl silicone oil provided by the invention is suitable for preparing a release agent for high-speed coating, and has a better anti-fogging effect.

Description

Technical Field

[0001] The invention relates to the field of organic silicon materials, and in particular to a branched vinyl silicone oil composition and a preparation method thereof, and an anti-atomization release agent. Background Art

[0002] With the growth of the release agent market demand, increasing the coating speed has become an important means for related companies to reduce costs and increase efficiency. In the past few years, the coating speed of 200m / min may be considered the industry standard; but with the improvement of the domestic solvent-free coating machinery manufacturing level, the operating speed of new equipment can 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 restricted the development of the industry and has become an urgent problem to be solved in the industry. The mechanism of the "atomization" phenomenon during high-speed coating is mainly that the centrifugal force generated by the rotation of the coating head "throws out" some small molecule silicone oil in the release agent, thereby forming mist. This mist not only poses a hidden danger to the health of operators, but also accumulates on the coating machine and the workshop floor, causing production safety accidents and shortening the service life of the coating machine.

[0004] CN115785452A discloses an anti-fog additive for release agent coating and a preparation method thereof. The anti-fog additive comprises at least a graft of hydrogenated silicone oil and vinyl silicone oil, wherein the vinyl silicone oil comprises at least a branched vinyl silicone oil; in addition, the branched vinyl silicone oil is capped by a trialkoxysilane group, and the hydrogenated silicone oil is capped by a trialkoxysilane group. When the anti-fog additive provided by the technical solution is applied to the release agent, it has an obvious effect of inhibiting the atomization phenomenon, but too high or too low overall viscosity will have a certain impact on the peel strength of the release agent.

[0005] At present, the industry mostly adopts the method of adding inhibitors to suppress or weaken the atomization phenomenon of release agents during high-speed coating, but this solution inevitably introduces new impurities, resulting in the application performance or coating effect of the release agent being affected. 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] In view of the deficiencies in the prior art, one of the objects of the present invention is to provide a branched vinyl silicone oil composition and a preparation method thereof, wherein the branched vinyl silicone oil composition comprises a branched vinyl silicone oil and a small amount of micro-crosslinked body, and has the characteristics of ultra-low acid value, low impurity ion content, high stability, etc.

[0007] The second object of the present invention is to provide an anti-fogging release agent, comprising the above-mentioned branched vinyl silicone oil composition.

[0008] To achieve the above purpose, 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, which includes a branched vinyl silicone oil having a structure shown in the following 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 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 10-200, preferably an integer from 20-200.

[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.; n can be selected from 10, 30, 50, 70, 100, 120, 150, 180, 200, etc.

[0015] In one embodiment, in the branched vinyl silicone oil having the structure shown in Formula I, the component proportion when b=2-4 is 12-30wt%, for example, 12wt%, 15wt%, 18wt%, 20wt%, 23wt%, 25wt%, 28wt%, 30wt%, 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 0.01-0.1wt% of a micro-crosslinked body, such as 0.01wt%, 0.02wt%, 0.04wt%, 0.06wt%, 0.08wt%, 0.1wt%, etc., and the micro-crosslinked body has a structure shown in Formula II below:

[0017] (R 1 (R 2 2SiO) n R 2 2SiO) c (SiO2) d (Ⅱ);

[0018] In the formula, R1 For vinyl, R 2 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 10-200.

[0021] Specifically, in the structure shown in Formula II, the c value can be 6, 7, 8, 9, 10, 11, 12, etc., the d value 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 acid value of the branched vinyl silicone oil composition is ≤0.001 mgKOH / g.

[0023] In one embodiment, the branched vinyl silicone oil composition has an impurity ion content of ≤10 ppm;

[0024] The impurity ions include potassium, sodium, sulfonate, etc. Such ions mainly come from acidic catalysts, alkaline neutralizers and filter aids introduced during the preparation process. The presence of these ions will affect the neutralization effect and 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] In a second aspect, the present invention provides a method for preparing the above-mentioned branched vinyl silicone oil composition, comprising the following steps:

[0026] 1) mixing part of the silicate with an acid catalyst A and deionized water A for hydrolysis reaction, and then adding a vinyl end-capping agent and the remaining silicate, acid catalyst B and deionized water B for hydrolysis-condensation reaction;

[0027] 2) The reaction liquid of step 1) is distilled to remove light components, then an acid auxiliary is added to carry out an aging reaction, and then an alkali solution is added to adjust the pH value to 5-7, and after washing with water, a branched siloxane small molecule is obtained;

[0028] 3) The branched siloxane small molecule of step 2) is mixed with a siloxane ring body and an acidic catalyst to carry out a ring-opening equilibrium reaction, and then a neutralizing agent is added to carry out a neutralization reaction, and the branched vinyl silicone oil composition is obtained by filtering.

[0029] In one embodiment, the silicate in step 1) is selected from one or both of methyl orthosilicate and ethyl orthosilicate, preferably ethyl orthosilicate; the silicates added twice may be the same or different;

[0030] The acid catalyst A and the acid catalyst B are selected from one or more of sulfuric acid, trifluoromethanesulfonic acid, and hydrochloric acid, preferably trifluoromethanesulfonic acid; the acid catalyst A and the 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 mass of the partial silicate accounts for 0.5-5% of the total mass of the silicate;

[0034] The amount of the acid catalyst A is 0.02-2% of the mass of the part of the silicate, such as 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 the acid catalyst B is 0.05-0.2% of the mass of the vinyl end-capping agent and the remaining silicate, such as 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 part of the silicate, for example 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, etc.; the amount of deionized water B added is 2.5-4 times of the molar amount of the remaining silicate, for example 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 performed 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 the time is 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°C, such as 70°C, 72°C, 75°C, 77°C, 80°C, 82°C, 85°C, etc., preferably 78-85°C, and 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, the deionized water A and B are gradually added to the reaction system, for example, continuously or in batches or dropwise, and there is no special requirement for the addition time;

[0039] Preferably, the deionized water B is added dropwise, the adding temperature is 30-85°C, for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 85°C, etc., preferably 60-80°C, the adding time is 0.1-1h, for example 0.1h, 0.2h, 0.4h, 0.6h, 0.8h, 1h, etc., preferably 0.2-0.5h, the adding is to complete the insulation reaction, that is, the adding time is not included in the above reaction time.

[0040] In one embodiment, the acid 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 the acid additive added is 2-20% of the total mass of the end-capping agent and the remaining silicate in step 1);

[0042] The alkali solution is selected from one or more of sodium carbonate solution and sodium bicarbonate solution, preferably sodium carbonate solution;

[0043] Preferably, the alkali 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, wherein the distillation temperature is 100-140° C. and the time is 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, end-capping monomers, etc.

[0046] In one embodiment, in step 2), the aging reaction has a reaction 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 a reaction time of 2-6h, such as 2h, 3h, 4h, 5h, 6h, etc., preferably 3-4h.

[0047] After the aging reaction in step 2) of the present invention is completed, it also includes treatment processes such as adding alkali solution to adjust the pH and washing with water, which are all conventional operations in the field and are not specifically limited by the present invention. For example, washing with deionized water is performed 2-6 times (preferably 3-4 hours).

[0048] The branched siloxane small molecule obtained in step 2) of the present invention has a structure shown in the following formula III:

[0049] (R 1 R2 2SiO 1 / 2 ) a (SiO2) b (III);

[0050] In the formula, R 1 For vinyl, R 2 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 the above formula III is:

[0053]

[0054] Furthermore, the branched siloxane small molecule obtained in step 2) also has a structure shown in the following formula IV:

[0055] (R 1 R 2 2SiO) c (SiO2) d (IV)

[0056] In the formula, R 1 For vinyl, R 2 is methyl;

[0057] The value of c is an even number selected from 6-12, and the value of d is an integer selected from 3-6.

[0058] In one embodiment, the siloxane ring body in step 3) is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and a dimethylsiloxane mixed ring body, preferably octamethylcyclotetrasiloxane;

[0059] The acidic catalyst is selected from one or more of sulfonic acid resin, trifluoromethanesulfonic acid, and sulfuric acid, preferably trifluoromethanesulfonic acid;

[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 molecules to the siloxane ring bodies 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 the acidic catalyst added is 0.01-0.3wt%, such as 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, etc., based on the total mass of the system;

[0063] The addition amount of the neutralizer is 0.2-2wt%, such as 0.2wt%, 0.5wt%, 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, etc., preferably 5-10wt%, based on the total mass of the system.

[0064] In one embodiment, the ring-opening equilibrium reaction in step 3) has a reaction 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 a reaction time of 4-8h, such as 4h, 5h, 6h, 7h, 8h, etc.;

[0065] The neutralization reaction has a reaction temperature of 10-40°C, such as 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc., preferably 30-40°C, and a reaction time of 0.5-4h, such as 0.5h, 1h, 2h, 3h, 4h, preferably 2-3h.

[0066] In one embodiment, the filtration in step 3) can be carried out with the aid of a filter aid, and after the filtration is completed, post-processing operations such as deashing can also be included, all of which can be carried out in conventional ways in the field without special requirements;

[0067] Preferably, the filter aid is diatomaceous earth, and more preferably, two diatomaceous earths with different particle sizes are used as filter aids, and the mass ratio of the two diatomaceous earths with different particle sizes is preferably in the range of 0.8-1.2:1; the specific particle sizes of the two diatomaceous earths are not limited, and can be selected within the particle size range conventionally used in the field. For example, one specific operation method is to select two diatomaceous earth particle sizes, preferably one large and one small, first mix the large-particle diatomaceous earth, mix for 0.5h, and then mix the small-particle diatomaceous earth, mix evenly and then perform filter pressing uniformly; in addition, the diatomaceous earth must be added to the system after the neutralization process is completed to avoid the unneutralized acid being adsorbed by the diatomaceous earth, and then being squeezed out in the subsequent filter pressing process and remaining in the system.

[0068] The above operations described in the preparation method of the present invention can be carried out in a protective gas environment, such as nitrogen.

[0069] In a third aspect, the present invention also provides use of the branched vinyl silicone oil composition in the preparation of a release agent.

[0070] An anti-fogging release agent includes the branched vinyl silicone oil composition of the present invention, specifically, is prepared from raw materials including the following parts by weight:

[0071] 100 parts of branched vinyl silicone oil composition,

[0072] 3-4 parts of hydrogen silicone oil;

[0073] 0.5-4 parts of platinum catalyst.

[0074] The specific type of the hydrogen-containing silicone oil is not limited, for example, it 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., preferably 20 viscosity high hydrogen-containing silicone oil;

[0075] The platinum catalyst is a conventional one in the field and has no special requirements in the present invention. For example, it can be selected from isopropanol-based Custer catalyst (Pt-5000), xylene-based Custer catalyst (Pt-5000), etc., preferably isopropanol-based Custer catalyst (Pt-5000).

[0076] The above components are mixed according to the proportion to obtain a slurry, namely the anti-atomization release agent. When used, the slurry is quickly coated with a roller (the coating speed is gradually increased).

[0077] The anti-fogging release agent provided by the present invention comprises the above-mentioned branched vinyl silicone oil composition. The anti-fogging effect thereof is mainly achieved through two aspects:

[0078] 1) Controlling the acid value and impurity ion content in the branched vinyl silicone oil composition within a certain content range can weaken the side reactions of the silicone oil product during the reaction and storage process, especially inhibiting 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 produce atomization, and weakening the probability and degree of atomization during the coating process;

[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-crosslinked bodies), thereby improving the adhesion of the silicone oil, and after the grafting reaction with the hydrogen-containing silicone oil, a silicone oil form with a similar network structure is obtained, which plays a role similar to a protective net during the release agent coating process, increasing the difficulty of the silicone oil small molecules being thrown out to a certain extent, thereby weakening the atomization phenomenon during the coating process.

[0080] Compared with modern technologies, the beneficial effects of the present invention are:

[0081] In the present invention, by reducing the acid value and impurity ion content in the silicone oil product and increasing the branching degree of the silicone oil, when the branched vinyl silicone oil is used to prepare a release agent, the prepared release agent has an obvious anti-fogging effect during high-speed coating. DETAILED DESCRIPTION

[0082] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0083] Unless otherwise specified, the reagents, materials and instruments used in the following examples are conventional reagents, conventional materials and conventional instruments in the art and can be obtained commercially.

[0084] In each embodiment and comparative example of the present invention, the sources of the main raw materials used are as follows:

[0085]

[0086]

[0087] The main analytical methods used in the examples and comparative examples of the present 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 test method: Inductively coupled plasma mass spectrometry is used to test the ion content;

[0090] Small molecule classification determination method: Nuclear magnetic resonance analysis is used to characterize the classification and structure of each component in the sample;

[0091] Volatile matter test method: high temperature difference subtraction method (150℃, 3g, 3h), that is, weigh 3g of sample and put it into a container with a specific mass mg, dry it at 150℃ for 3h, and 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 light component content in the sample;

[0092] Sample aging test: 100g of sample was sealed and stored in a 50℃ oven for aging test for 3 months;

[0093] Anti-fogging performance measurement: In a clean environment, an aerosol detector is used to measure whether aerosol is detected at a certain linear speed to determine its anti-fogging performance.

[0094] Example 1

[0095] A method for preparing branched vinyl silicone oil, the specific steps are as follows:

[0096] 1) Under nitrogen atmosphere, 2.2 g (0.01056 mol) of ethyl 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 hydrolysis reaction for 5 min;

[0097] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of ethyl orthosilicate and 0.29 g of trifluoromethanesulfonic acid were added and mixed evenly, and the mixture was heated to 70° C., and 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system for 0.2 h; and then, the mixture was subjected to a hydrolysis-condensation reaction at 80° C. for 4 h.

[0098] 2) removing light components by distillation at 120° C. for 3 h until the light components no longer flow out, at which point the light component content in the system is reduced to less than 0.5 wt %;

[0099] Then, 18 g of acetic acid was added, and the mixture was aged at 90° C. for 4 h. Then, a 5 wt% sodium bicarbonate solution was added to adjust the pH value to 6, and the mixture was allowed to stand, separated, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated, and the lower aqueous phase was removed. This operation was repeated three times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0100] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; a value is 4-6, b value is 1-2, c value is 8, and d value is 4.

[0101] The results of NMR characterization are: 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 970 g (3.27 mol) of octamethylcyclotetrasiloxane were added to a four-necked flask, and then 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, heated to 50° C. for ring-opening equilibrium reaction for 5 h, and then 1 wt% of calcium carbonate was added to the system, neutralized at 30° C. for 2 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 1:1) were added in sequence, and mixed for 0.5 h; filtered and de-lightened to obtain a branched vinyl silicone oil composition;

[0103] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the component content of b=2 accounts for 20wt%; wherein,

[0104] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.95wt%: In Formula I, R 1 For vinyl, R 2 is methyl; a is 4-6, b is 1-2; n is 24-44;

[0105] The content of the micro-crosslinked body shown in Formula II is 0.05wt%: In Formula II, R 1 For vinyl, R 2 is methyl; c is 8, d is 4; n is 24-44.

[0106] Example 2

[0107] This embodiment provides a method for preparing a branched vinyl silicone oil, and the specific steps are as follows:

[0108] 1) Under nitrogen atmosphere, 2.2 g (0.0106 mol) of ethyl orthosilicate was mixed with 0.001 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and heated to 40°C for hydrolysis reaction for 20 min;

[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 evenly, and the mixture was heated to 75°C. 28 g (1.5556 mol) of deionized water was slowly added dropwise to the above system for 0.3 h. The mixture was then subjected to a hydrolysis-condensation reaction at 82°C for 5 h.

[0110] 2) removing light components by distillation at 120° C. for 4 h until the light components no longer flow out, at which point the light component content in the system is reduced to less than 0.4 wt %;

[0111] Then, 22.2 g of propionic acid was added, and the mixture was aged at 110° C. for 2 h. Then, a 5 wt% sodium bicarbonate solution was added to adjust the pH value to 7, and the mixture was allowed to stand, separated, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated, and the lower aqueous phase was removed. This operation was repeated four times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0112] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 700 g (2.3599 mol) of octamethylcyclotetrasiloxane were added to a four-necked flask, and then 0.02 wt% of trifluoromethanesulfonic acid was added to the system, mixed, heated to 70°C for ring-opening equilibrium reaction for 8 h, and then 2 g of calcium carbonate with a mass proportion of 0.3 wt% was added to the system, neutralized at 20°C for 4 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 0.8:1) were added in sequence, and mixed for 0.5 h; filtered and light removed to obtain a branched vinyl silicone oil composition;

[0114] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the content of the component b=2-3 accounts for 25wt%; wherein

[0115] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.97 wt %: In Formula I, R 1 For vinyl, R 2 is methyl; 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 0.03wt%: In Formula II, R 1 For vinyl, R 2 is methyl; c is 8-10, d is 4-5; n is 14-34.

[0117] Example 3

[0118] This embodiment provides a method for preparing a branched vinyl silicone oil, and the specific steps are as follows:

[0119] 1) Under nitrogen atmosphere, 1.1 g (0.0053 mol) of ethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.05 g (0.0028 mol) of deionized water, and heated to 35°C for hydrolysis reaction for 5 min;

[0120] Then, 190 g (1.0193 mol) of tetramethyldivinyldisiloxane, 109.1 g (0.5237 mol) of ethyl orthosilicate and 0.29 g of trifluoromethanesulfonic acid were added and mixed evenly, and the mixture was heated to 70°C. 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system for 0.2 h. The mixture was then subjected to a hydrolysis-condensation reaction at 80°C for 4 h.

[0121] 2) removing light components by distillation at 120° C. for 3 h until the light components no longer flow out, at which point the light component content in the system is reduced to less than 0.5 wt %;

[0122] Then, 18 g of acetic acid was added, and the mixture was aged at 90° C. for 4 h. Then, a 5 wt% sodium carbonate solution was added to adjust the pH value to 6, and the mixture was allowed to stand, separated, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated, and the lower aqueous phase was removed. This operation was repeated three times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0123] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 1300 g (4.3827 mol) of dimethylsiloxane mixed rings were added to a four-necked flask, and 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, and then 1.5 wt% of calcium carbonate was added to the system, and neutralized at 35° C. for 3 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 1.2:1) were added in sequence, and mixed for 0.5 h; filtered and de-lightened to obtain a branched vinyl silicone oil composition;

[0125] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the component content of b=2 accounts for 21wt%; wherein

[0126] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.97 wt %: In Formula I, R 1 For vinyl, R 2 is methyl; 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 0.03wt%: In Formula II, R 1 For vinyl, R 2 is methyl; c is 8, d is 4; n is 35-55.

[0128] Example 4

[0129] This embodiment provides a method for preparing a branched vinyl silicone oil, and the specific steps are as follows:

[0130] 1) Under nitrogen atmosphere, 2.2 g (0.0106 mol) of ethyl 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 hydrolysis reaction for 10 min;

[0131] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of ethyl orthosilicate and 0.29 g of trifluoromethanesulfonic acid were added and mixed evenly, and the mixture was heated to 70°C. 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system for 0.4 h. The mixture was then subjected to a hydrolysis-condensation reaction at 85°C for 2 h.

[0132] 2) The reaction solution was distilled at 100° C. to remove light components for 4 hours until the light components no longer flowed out, at which point the light component content in the system was reduced to less than 0.5 wt %;

[0133] Then, 6 g of acetic acid was added, and the mixture was aged at 140° C. for 6 h. Then, a 6 wt% sodium bicarbonate solution was added to adjust the pH value to 7, and the mixture was allowed to stand, separated, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated, and the lower aqueous phase was removed. This operation was repeated three times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0134] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 1600 g (5.3941 mol) of dimethylsiloxane mixed ring were added to a four-necked flask, and then 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, heated to 65 ° C for ring-opening equilibrium reaction for 6 h, and then 16 g of calcium carbonate with a mass proportion of 1 wt% was added to the system, neutralized at 40 ° C for 4 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two is 1:1) were added in sequence, and mixed for 0.5 h; filtered and de-lightened to obtain a branched vinyl silicone oil composition;

[0136] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the content of the component b=2 accounts for 18wt%; wherein

[0137] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.93wt%: In Formula I, R 1 For vinyl, R 2 is methyl; a is 4-6, b is 1-2; n is 46-66;

[0138] The content of the micro-crosslinked body shown in Formula II is 0.07wt%: In Formula II, R 1 For vinyl, R 2is methyl; c is 8, d is 4; n is 46-66.

[0139] Example 5

[0140] This embodiment provides a method for preparing a branched vinyl silicone oil, and the specific steps are as follows:

[0141] 1) Under nitrogen atmosphere, 4.4 g (0.0211 mol) of ethyl 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 hydrolysis reaction for 5 min;

[0142] Then, 160 g (0.8584 mol) of tetramethyldivinyldisiloxane, 105.8 g (0.5078 mol) of ethyl orthosilicate and 0.29 g of trifluoromethanesulfonic acid were added and mixed evenly, and the mixture was heated to 70°C. 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system for 0.2 h. The mixture was then subjected to a hydrolysis-condensation reaction at 80°C for 4 h.

[0143] 2) removing light components by distillation at 120° C. for 3 h until the light components no longer flow out, at which point the light component content in the system is reduced to less than 0.5 wt %;

[0144] Then, 18 g of acetic acid was added, and the mixture was aged at 90° C. for 4 h. Then, a 5 wt% sodium carbonate solution was added to adjust the pH value to 6, and the mixture was allowed to stand, separated into layers, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated into layers, and the lower aqueous phase was removed. This operation was repeated three times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0145] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 970 g (3.2702 mol) of dimethylsiloxane mixed rings were added to a four-necked flask, and then 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, heated to 55° C. for ring-opening equilibrium reaction for 7 h, and then 1 wt% of calcium carbonate was added to the system, neutralized at 30° C. for 1 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 1:1) were added in sequence, and mixed for 0.5 h; filtered and de-lightened to obtain a branched vinyl silicone oil composition;

[0147] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the content of the component b=2-3 accounts for 28wt%; wherein

[0148] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.91wt%: In Formula I, R 1 For vinyl, R 2 is methyl; 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 0.09wt%: In Formula II, R 1 For vinyl, R 2 is methyl; c is 6-10, d is 3-5; n is 24-44.

[0150] Example 6

[0151] This embodiment provides a method for preparing a branched vinyl silicone oil, and the specific steps are as follows:

[0152] 1) Under nitrogen atmosphere, 2.2 g (0.0106 mol) of ethyl orthosilicate was mixed with 0.002 g of trifluoromethanesulfonic acid and 0.1 g (0.0056 mol) of deionized water, and heated to 30°C for hydrolysis reaction for 25 min;

[0153] Then, 177 g (0.9496 mol) of tetramethyldivinyldisiloxane, 108 g (0.5184 mol) of ethyl orthosilicate and 0.29 g of trifluoromethanesulfonic acid were added and mixed evenly, and the mixture was heated to 70°C. 24 g (1.3333 mol) of deionized water was slowly added dropwise to the above system for 0.3 h. The mixture was then subjected to a hydrolysis-condensation reaction at 78°C for 6 h.

[0154] 2) removing light components by distillation at 140° C. for 2 h until the light components no longer flow out, at which point the light component content in the system is reduced to less than 0.5 wt %;

[0155] Then, 50 g of acetic acid was added, and the mixture was aged at 80° C. for 2 h. Then, a 4 wt% sodium carbonate solution was added to adjust the pH value to 6, and the mixture was allowed to stand, separated, and the lower aqueous phase was removed. 30 g of deionized water was added, and the mixture was mixed for 0.5 h. The mixture was allowed to stand, separated, and the lower aqueous phase was removed. This operation was repeated three times. After that, the light acid components were removed by high-temperature distillation (120° C., 4 h), and a branched siloxane small molecule was obtained.

[0156] Branched siloxane small molecules include structures shown in formula III and IV, wherein R 1 For vinyl, R 2 is methyl; 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 (mixture, a total of about 0.096 mol) of branched siloxane small molecules and 970 g (3.2702 mol) of dimethylsiloxane mixed rings were added to a four-necked flask, and then 1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, heated to 55°C for ring-opening equilibrium reaction for 7 hours, and then 2 wt% of sodium carbonate was added to the system, neutralized at 40°C for 4 hours, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 1:1) were added in sequence, and mixed for 0.5 hours; filtered and de-lightened to obtain a branched vinyl silicone oil composition;

[0158] The branched vinyl silicone oil composition has a branched vinyl silicone oil with a structure shown in Formula I, and the content of the component with b=2 accounts for 16wt%; wherein

[0159] The content of the branched vinyl silicone oil of the structure shown in Formula I is 99.95wt%: In Formula I, R 1 For vinyl, R 2 is methyl; a is 4-6, b is 1-2; n is 24-44;

[0160] The content of the micro-crosslinked body shown in Formula II is 0.05wt%: In Formula II, R 1 For vinyl, R 2 is methyl; c is 8, d is 4; n is 24-44.

[0161] Comparative Example 1

[0162] A linear vinyl silicone oil was prepared by referring to the method of 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 a capping agent. The specific steps were as follows: 1) Under a nitrogen atmosphere, 35.8 g (0.1921 mol) of tetramethyldivinyldisiloxane and 970 g (3.2702 mol) of dimethylsiloxane were added to a four-necked flask to mix the rings, and then 0.1 wt% of trifluoromethanesulfonic acid was added to the system, mixed, and the temperature was raised to 55°C for a ring-opening equilibrium reaction for 7 h, and then 1 wt% of calcium carbonate was added to the system, and the reaction was neutralized at 30°C for 1 h, and then two diatomaceous earths (DZ1000 and 545RVS, the mass ratio of the two was 1:1) were added in sequence, and mixed for 0.5 h; filtration and light removal were performed to obtain a linear vinyl silicone oil composition;

[0163] The linear vinyl silicone oil composition has the following linear vinyl silicone oil structure:

[0164] R 1 R 2 2SiO(R 2 2SiO) n R2 2 R 1 ;

[0165] In the formula, R 1 For vinyl, R 2 is methyl; n is 58-78;

[0166] The compositions prepared in the above Examples 1-6 and Comparative Example 1 were subjected to parameter tests, and the test data results are shown in Table 1 below:

[0167] Table 1

[0168]

[0169] Application Examples 1-6

[0170] The anti-fogging release agent was prepared 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 of platinum catalyst (isopropanol system, Pt-5000ppm);

[0174] Wherein, the branched vinyl silicone oil composition is the branched vinyl silicone oil composition prepared in Examples 1-6 in sequence;

[0175] The above raw materials were mixed according to the formula to obtain a mixed slurry, which was then used as a release agent and quickly coated using a roller (gradually increasing the coating speed), while recording the conditions for the occurrence of aerosols in the surrounding environment. The results are shown in Table 2.

[0176] Application Comparative Example 1

[0177] According to the formulations of the above application examples 1-6, the difference is that the branched vinyl silicone oil composition is replaced by the vinyl silicone oil composition prepared in Comparative Example 1 in sequence, and other operations and conditions remain unchanged. The results are shown in Table 2.

[0178] Table 2 Performance test data of embodiments and comparative examples

[0179]

[0180]

[0181] By comparing the above data, it can be seen that the branched vinyl silicone oil composition provided by the present invention has high stability and has obvious anti-fogging performance when used in a release agent.

[0182] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A branched vinyl silicone oil composition, characterized in that: Including branched vinyl silicone oil having the structure shown in the following 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 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 10-200, preferably an integer from 20-200.

2. The branched vinyl silicone oil composition according to claim 1, characterized in that In the branched vinyl silicone oil having the structure shown in Formula I, the component with b=2-4 accounts for 12-30wt%, preferably 18-30%; and / or The branched vinyl silicone oil composition has an acid value of ≤0.001 mgKOH / g; and / or The branched vinyl silicone oil composition has an impurity ion content of ≤10 ppm.

3. The branched vinyl silicone oil composition according to claim 1 or 2, characterized in that: The branched vinyl silicone oil composition comprises 0.01-0.1 wt% of a micro-crosslinked body, and the micro-crosslinked body has a structure shown in the following formula II: (R 1 (R 2 2SiO) n R 2 2SiO) c (SiO2) d (Ⅱ); In the formula, R 1 For vinyl, R 2 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 10-200.

4. A method for preparing the branched vinyl silicone oil composition according to any one of claims 1 to 3, characterized in that: The following steps are involved: 1) mixing part of the silicate with an acid catalyst A and deionized water A for hydrolysis reaction, and then adding a vinyl end-capping agent and the remaining silicate, acid catalyst B and deionized water B for hydrolysis-condensation reaction; 2) The reaction liquid of step 1) is distilled to remove light components, then an acid auxiliary is added to carry out an aging reaction, and then an alkali solution is added to adjust the pH value to 5-7, and after washing with water, a branched siloxane small molecule is obtained; 3) The branched siloxane small molecule of step 2) is mixed with a siloxane ring body and an acidic catalyst to carry out a ring-opening equilibrium reaction, and then a neutralizing agent is added to carry out a neutralization reaction, and the branched vinyl silicone oil composition is obtained by filtering.

5. The method for preparing the branched vinyl silicone oil composition according to claim 4, characterized in that: Step 1) The silicate is selected from one or both of methyl orthosilicate and ethyl orthosilicate, preferably ethyl orthosilicate; The acid catalyst A and the acid catalyst B are selected from one or more of sulfuric acid, trifluoromethanesulfonic acid and hydrochloric acid, preferably trifluoromethanesulfonic acid; The vinyl end-capping agent is selected from one or more of tetramethyl divinyl disiloxane and vinyl-terminated silicone oil, preferably tetramethyl divinyl disiloxane; and / or Step 1) The molar ratio of the end-capping agent to the total silicate is 1.5-2:1, preferably 1.7-1.8:1; The mass of the partial silicate accounts for 0.5-5% of the total mass of the silicate; The amount of the acid catalyst A is 0.02-2% of the mass of the part of the silicate; the mass of the acid catalyst B is 0.05-0.2% of the sum of the mass of the vinyl end-capping agent and the remaining silicate; The amount of deionized water A added is 40-60% of the molar amount of part of the silicate; the amount of deionized water B added is 2.5-4 times, preferably 2.5-3 times, the molar amount of the remaining silicate.

6. The method for preparing the branched vinyl silicone oil composition according to claim 4, characterized in that: Step 1) The hydrolysis reaction is carried out at a temperature of 30-50°C and a time of 0.05-0.5h; and / or Step 1) The hydrolysis-condensation reaction is carried out at a temperature of 70-85°C, preferably 78-85°C, for 3-6 hours, preferably 4-5 hours; and / or Step 1) The deionized water A and B are gradually added to the reaction system; preferably, the deionized water B is added dropwise, the addition temperature is 30-85°C, preferably 60-80°C, and the addition time is 0.1-1h, preferably 0.2-0.5h.

7. The method for preparing the branched vinyl silicone oil composition according to claim 4, characterized in that: Step 2) the acid auxiliary agent is selected from one or more of sulfuric acid, acetic acid, and propionic acid, preferably acetic acid; and / or Step 2) The amount of the acid additive added is 2-20% of the total mass of the end-capping agent and the remaining silicate in step 1); and / or Step 2) the alkali solution is selected from one or more of sodium carbonate solution and sodium bicarbonate solution, preferably sodium carbonate solution; the alkali solution is an aqueous solution of alkali, and the concentration is preferably 4-6wt%; and / or Step 2) the reaction solution is distilled to remove light components, the distillation temperature is 100-140° C., the time is 2-4 hours, preferably 2-3 hours; and / or Step 2) The aging reaction has a reaction temperature of 80-140°C, preferably 80-100°C, and a reaction time of 2-6h, preferably 3-4h.

8. The method for preparing the branched vinyl silicone oil composition according to claim 4, characterized in that: Step 3) the siloxane ring body is selected from one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and a dimethylsiloxane mixed ring body, preferably octamethylcyclotetrasiloxane; The acidic catalyst is selected from one or more of sulfonic acid resin, trifluoromethanesulfonic acid, and sulfuric acid, preferably trifluoromethanesulfonic acid; The neutralizing agent is selected from one or more of calcium carbonate, sodium bicarbonate, and sodium carbonate, preferably calcium carbonate; and / or Step 3) the molar ratio of the branched siloxane small molecule to the siloxane ring body is 1:20-60; The amount of the acidic catalyst added is 0.01-0.3wt%, based on the total mass of the system; The addition amount of the neutralizing agent is 0.2-2 wt %, preferably 5-10 wt %, based on the total mass of the system.

9. The method for preparing the branched vinyl silicone oil composition according to claim 4, characterized in that: Step 3) the ring-opening equilibrium reaction, the reaction temperature is 30-70°C, the reaction time is 4-8h; and / or Step 3) the neutralization reaction, the reaction temperature is 10-40°C, preferably 30-40°C, the reaction time is 0.5-4h, preferably 2-3h; and / or The filtration in step 3) is carried out with the aid of a filter aid; Preferably, the filter aid is diatomaceous earth, and more preferably, two diatomaceous earths with different particle sizes are used as the filter aid.

10. An anti-atomization release agent, characterized in that: A branched vinyl silicone oil composition comprising the branched vinyl silicone oil composition according to any one of claims 1 to 3 or a branched vinyl silicone oil composition prepared by the method according to any one of claims 4 to 9, specifically, prepared from raw materials comprising the following parts by weight: 100 parts of branched vinyl silicone oil composition, 3-4 parts of hydrogen silicone oil; 0.5-4 parts of platinum catalyst.

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