Manufacturing process for cyanoethyltrimethoxysilane and dimer

Abstract

The process for preparing a reaction product containing cyanoethyltrimethoxysilane and a dimer is carried out via the reaction of cyanoethyltriethoxysilane with methanol and water in the presence of a catalyst. The reaction product is useful as an adhesion promoter, coupling agent, or crosslinking agent. The reaction product may be incorporated into a polyorganosiloxane sealant composition.

Description

【Technical Field】 【0001】 (Cross - reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 466,735, filed May 16, 2024, under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 63 / 466,735 is incorporated herein by reference. 【0002】 (Field of the Invention) The present invention relates to a process for producing a reaction product containing cyanoethyltrimethoxysilane and its dimer. The present invention further relates to a polyorganosiloxane composition containing the reaction product. 【Background Art】 【0003】 Introduction U.S. Patent No. 3,008,975 discloses a process for preparing silicon esters from halosilanes.... A mixture of halosilane and alcohol is formed, the pressure applied to the mixture is reduced to about 200 mmHg absolute pressure, and the mixture is maintained at a temperature at which the halosilane and alcohol react in the liquid phase to produce a silicon ester.... One of the by - products of esterification is water. Water is a highly undesirable by - product. Because it hydrolyzes the halosilane present in the system to produce undesirable polysiloxanes, combines with hydrogen halide to produce hydrohalic acid, which attacks certain acid - sensitive groups that may be present on the silane,... and catalyzes other undesirable side reactions.... Therefore, it is desirable to remove water from the reaction system. 【0004】 Cyanoethyltrimethoxysilane (CETMS) is useful as an adhesion promoter or coupling agent in siloxane compositions, such as room-temperature vulcanizable (RTV) polyorganosiloxane sealant compositions. CETMS can be prepared via a hydrosilylation reaction of acrylonitrile with trichlorosilane, followed by methoxylation. CETMS can also be prepared by a hydrosilylation reaction of trimethoxysilane with acrylonitrile. However, these processes have the disadvantage of making CETMS not widely available on a commercial scale. [Overview of the Initiative] 【0005】 The process for producing a reaction product containing an alkoxysilane product and a dimer (composition) involves combining cyanoethyltriethoxysilane, methanol, water, and an acid catalyst. The composition is useful for polyorganosiloxane compositions. [Modes for carrying out the invention] 【0006】 More specifically, the process for producing reaction products including alkoxysilane products and dimers (compositions) is: 1) Combining starting materials comprising (A) cyanoethyltriethoxysilane (CETES), (B) a stoichiometric excess amount of methanol, (C) water, and (D) an acid catalyst, thereby generating a reaction mixture. Optionally, 2) add (E) activated carbon to the reaction mixture, 3) Remove the material containing methanol, ethanol, and (D) acid catalyst from the reaction mixture, 4) Repeating steps 1) to 3) once or more (adding (B) methanol, (C) water, and (D) acid catalyst in total at least twice, and then removing methanol, ethanol, and catalyst), thereby forming a composition. 【0007】 In this process, the transesterification reaction between CETES and methanol and the hydrolysis reaction to form a dimer may proceed according to the reaction scheme shown below. 【0008】 [ka] In the formula for the alkoxysilane product, when x=0, this formula is CETMS. However, partially methoxylated species, such as cyanoethyl-,diethoxy-,monomethoxysilane (when x=2) and / or cyanoethyl-,monoethoxy-,dimethoxysilane (when x=1), can also be formed during the process described herein. Thus, the subscript x can have values ​​from 0 to 2, alternatively from 0 to 1, and alternatively from 0. In the formula for the dimer in this reaction scheme, each R is independently selected from the group consisting of methyl and ethyl. Alternatively, each R may be methyl. When the reaction product is used in a polyorganosiloxane composition, it is desirable to drive the reaction to a high conversion rate of ethoxy groups to methoxy groups in CETES, and to form a dimer in an amount that improves one or more properties of the polyorganosiloxane composition and / or its cured product. 【0009】 In step 1) of the process described herein, (A) cyanoethyltriethoxysilane and (B) methanol are used in amounts sufficient to give a stoichiometric excess of methanol. The amounts of (A) cyanoethyltriethoxysilane and (B) methanol may be at least 5:1 (B):(A) (molar ratio), alternatively at least 15:1, while at the same time, the (B):(A) ratio may be up to 30:1, alternatively up to 15:1. Alternatively, the (B):(A) ratio may be 5:1 to 30:1, alternatively >5:1 to 30:1, and alternatively 15:1 to 30:1. 【0010】 While we do not wish to be bound by theory, it is conceivable that step 1) can be carried out at room temperature or at high temperatures, such as up to 70°C. Alternatively, the temperature may be between 21°C and 70°C. The time for the transesterification reaction in step 1) is sufficient to reach equilibrium. For example, at room temperature, the time may be between 1 and 4 hours. However, the exact time will depend on various factors such as the selected temperature and the selection and amounts of (C) water and (D) acid catalysts. While we do not wish to be bound by theory, it is conceivable that carrying out step 1) may be efficient in terms of time, energy, and cost associated with heating and cooling. The use of an acid catalyst may offer the advantage of enabling a rapid reaction at room temperature, which minimizes time and operational costs. The reaction may be optionally carried out at high temperatures. 【0011】 The starting material (C), water, is generally not limited and may be pure (i.e., free from or substantially free from minerals and / or other impurities). Alternatively, the water may be treated or untreated before its addition in step 1) described above. Examples of processes that may be used to purify the water include distillation, filtration, deionization, and combinations of two or more of these, thereby deionizing, distilling, and / or filtering the water. Alternatively, the water may be untreated (e.g., tap water, i.e., water supplied by a city water system, or well water used without further purification). 【0012】 Water may be used in an amount selected by those skilled in the art, depending on various factors, such as the desired amount of dimer formed in the reaction product, the reaction parameters employed, the scale of the reaction, and the type of (D) acid catalyst selected. However, the amount of (C) water may be 0.05% to 1% based on the weight of (B) methanol. 【0013】 The starting material (D), the acid catalyst, can be selected from the group consisting of, for example, a hydrogen halide of formula HX (wherein X is Cl, Br, or I), a sulfonic acid (such as toluenesulfonic acid or trifluoromethanesulfonic acid), and an ion exchange resin. Alternatively, the (D) acid catalyst may be a hydrogen halide, and alternatively, the acid catalyst may be HCl. When the (D) acid catalyst is a hydrogen halide, e.g., HCl, the hydrogen halide (e.g., HCl) may be used in amounts of at least 1 ppm, alternatively at least 5 ppm, alternatively at least 10 ppm, or alternatively at least 30 ppm, based on the combined weight of (A) CETES and (B) MeOH, while at the same time, the amount of hydrogen halide (e.g., HCl) may be up to 100 ppm, alternatively up to 50 ppm, or alternatively up to 30 ppm. Alternatively, the amount of hydrogen halide (e.g., HCl) may be 10 ppm to 100 ppm, 10 ppm to 50 ppm, or 30 ppm, on the same basis. Alternatively, if ion exchange resin is used, its amount may be at least 0.1% of the liquid, or 0.5% of the solid, on the same basis, while simultaneously being up to 30%. Alternatively, the amount of ion exchange resin may be 0.1% to 30%, on the same basis. 【0014】 The starting materials used in step 1) of this process are known in the art and commercially available. CETES is available from Gelest Inc. (Morrisville, Pennsylvania, USA). MeOH and HCl are available from various suppliers, including Sigma-Aldrich, Inc. (St. Louis, Missouri, USA). The ion exchange resins used herein may be strong acid and weak acid cation exchange resins in which the ionic form of the resin is not hydrogen (H+). Such ion exchange resins are commercially available, for example, DOWEX® Monosphere 2030, DOWEX® MARATHON® 1200 (Na+ type), and AMBERLITE IR122 Na from TDCC. 【0015】 The preparation of the starting materials in step 1) may be carried out in a batch or continuous manner by any convenient means such as mixing. Mixing may be carried out using conventional equipment such as a stirrer and optionally a batch reactor equipped with heating means such as a jacket. For example, if step 1) is carried out in batch mode, (A) CETES may be placed in the reactor with optionally stirring. Then, all or part of (B) methanol may be added to the reactor. Next, (C) water may be added to the reactor. Next, (D) acid catalyst may be added to the reactor. The acid catalyst may be added directly to the reactor. Alternatively, a catalyst solution may be formed by combining (B) methanol and (D) acid catalyst and this may be added to the reactor. 【0016】 Alternatively, the process can be carried out in a packed-bed reactor, for example, if a solid catalyst, such as an ion exchange resin, is used, the reactor can be packed with (D) an acid catalyst, and / or if step 2) is present, for example activated carbon can be used. 【0017】 Step 2) of the process includes (E) combining the activated carbon with the reaction mixture prepared in step 1). Step 2) is optional. However, if used, step 2) can be carried out at room temperature, for example, by mixing the activated carbon with the reaction mixture prepared in step 1) for a sufficient amount of time to adsorb the acid HCl from the reaction mixture. The exact time depends on various factors such as the size of the container used in step 2) (which may be the same as the reactor used in step 1), but the time may be at least 1 hour, alternatively at least 2 hours, alternatively at least 4 hours, alternatively at least 8 hours, or alternatively at least 16 hours, while at the same time, the time may be up to 48 hours, alternatively up to 24 hours, or alternatively up to 16 hours. Step 2) can be carried out under conditions that minimize or eliminate moisture. 【0018】 If step 2) is present, (E) activated carbon may be selected from the group consisting of (E1) bituminous activated carbon, (E2) coconut activated carbon having an iodine value of ≥1200 mg / g, and (E3) combinations of both (E1) and (E2). (E1) bituminous activated carbon and (E2) coconut activated carbon are known in the art and are commercially available from various suppliers such as General Carbon Corporation (Paterson, New Jersey, USA) or Calgon Carbon (Pittsburgh, Pennsylvania, USA). Bituminous activated carbon may have an iodine value of at least 500 mg / g(min), alternatively at least 600 mg / g(min), alternatively at least 750 mg / g(min), alternatively at least 850 mg / g(min), and alternatively at least 900 mg / g(min), while at the same time, bituminous activated carbon may have an iodine value of up to 1200 mg / g(min), alternatively up to 1100 mg / g(min), alternatively up to 1000 mg / g(min), and alternatively up to 950 mg / g(min). Alternatively, the iodine value of bituminous activated carbon may be 600 mg / g(min) to 1200 mg / g(min), alternatively 750 mg / g(min) to 1200 mg / g(min), 900 mg / g(min) to 1200 mg / g(min), or alternatively 900 mg / g(min) to 1050 mg / g(min). The iodine value of coconut activated carbon may be ≥ 1200 mg / g(min), alternatively 1200 mg / g(min) to 1500 mg / g(min), or alternatively 1200 mg / g(min) to 1300 mg / g(min). 【0019】 Examples of bituminous activated carbon include GC 12×40, a granular form of unused activated carbon with an iodine value of 900 mg / g(min) and a density of 0.47-0.53 g / cc, commercially available from General Carbon Corporation, and CAL(trademark) 12×40 granular activated carbon, a re-aggregated metallurgical grade bituminous carbon with an iodine value of 1000 mg / g(min), commercially available from Calgon Carbon. Other bituminous activated carbons from Calgon Carbon include CPG® LF 12×40 with an iodine value of 950 mg / g(min), FILTRASORB® 300M with an iodine value of 900 mg / g(min), FILTRASORB® 400M with an iodine value of 1000 mg / g(min), HPC MAXX with an iodine value of 900 mg / g, and SGL 8x20, a granular activated carbon made from bituminous carbon combined with a binder, with an iodine value of 900 mg / g. Coconut activated carbon includes OLC Plus 12×30 with an iodine value of 1200 mg / g(min) and a density of 0.45 g / cc, which is also available from Calgon Carbon. 【0020】 If step 2) is present (i.e., activated carbon is used), the activated carbon may be treated before use or may be untreated. Water adsorbed on activated carbon may form additional dimers. Alternatively, the process may further include treating the activated carbon before use in step 2). The treatment may be carried out, for example, to dry the activated carbon (e.g., to remove all or part of any adsorbed water to minimize the possibility of hydrolysis of the alkoxysilane product when the carbon comes into contact with the transesterification mixture). For example, the activated carbon may be heated to a temperature above the boiling point of water (e.g., >100°C, alternatively >100°C to 200°C, or alternatively 120°C to 160°C) for a sufficient time, e.g., 1 minute to 24 hours, to remove all or part of the water. The activated carbon may be heated under ambient pressure or reduced pressure. The activated carbon may be heated and stored under an inert atmosphere such as nitrogen before use in step 2) so that the amount of water used in the process to form dimers is controlled. 【0021】 Step 3) of the process includes removing (excess) unreacted (B) methanol, ethanol (produced as a by-product), and (D) acid catalyst from the reaction mixture. Step 3) may be carried out by any convenient means. Step 3) may also include filtration to remove solid materials such as ion exchange resin when used as (D) acid catalyst, and / or activated carbon when step 2) is present. Step 3) may also include stripping and / or distillation under heating and optionally under reduced pressure to remove methanol, ethanol, and liquid acid catalysts such as HCl. 【0022】 Step 4) of this process includes repeating steps 1) to 3) one or more times. Step 4) may alternatively include repeating 1) to 3) at least once, alternatively 1 to 4 times. Without wishing to be bound by theory, if steps 1) to 3) of adding water, methanol and an acid catalyst and subsequent removal are repeated too many times (for example, more than five times (alternatively five or more times), a total of 6 to 7 times or more), it may result in an increase in the cost that makes the process non - practical on a commercial scale. Alternatively, step 4) may include repeating steps 1) to 3) once or twice, especially when step 2) is present. Without wishing to be bound by theory, due to thermodynamic equilibrium limitations and the volatility of methanol being higher than ethanol, during step 3) (for example, via stripping and / or distillation), a reverse reaction may occur through the reaction between CETMS (when x = 0 in the formula of the alkoxylated product shown above) or partially methoxylated species (when x = 1 or 2) and the EtOH by - product (which cannot be removed until all or most of the lower - boiling MeOH is first removed). Without being bound by theory, it is considered that this reverse reaction can be minimized by treating the reaction mixture with activated carbon in step 2). Since each repetition of steps 1) to 3) can increase the cost of the process, it is desirable to minimize the number of repetitions in step 4) while achieving the yield and purity of the reaction product under the condition of efficiency. 【0023】 The above - mentioned process may optionally further include one or more additional steps. For example, after step 4), the process may further include 5) treating the reaction product with activated carbon. Without wishing to be bound by theory, step 5) may be carried out by pumping the reaction product through a container such as a drum or bed containing activated carbon, or adding activated carbon to the container used in step 4) and then filtering it from the product. The activated carbon used in step 5) may be the same as that described above with respect to step 2). If step 5) is present, the process may optionally further include drying the activated carbon before use. 【0024】 The above process is the formula 【0025】 【Chemical formula】 of the alkoxysilane product and the formula 【0026】 【Chemical formula】 a dimer of, wherein R and x are as described above, to produce a composition comprising the dimer. Alternatively, each R can be methyl. Alternatively, each x can be 0. Alternatively, the composition is the formula 【0027】 【Chemical formula】 having cyanoethyltrimethoxysilane (CETMS) and the formula 【0028】 【Chemical formula】 It may include a dimer having the same. Alternatively, the composition may consist essentially of CETMS and its dimer. Alternatively, the composition may consist essentially of CETMS and its dimer. Alternatively, the composition may be substantially free of methoxy groups in the alkoxysilane product and dimer, or free of them. In the process described above, the conversion rate of ethoxy groups to methoxy groups in the CETES starting material is measured by the test method described below and, when used in the examples, may be at least 90 GC area%, alternatively at least 91 GC area%, alternatively at least 92 GC area%, alternatively at least 93 GC area%, and alternatively at least 94 GC area%, while at the same time, the conversion rate may be up to 100 GC area%, alternatively up to 99 GC area%, alternatively up to 98 GC area%, alternatively up to 97 GC area%, and alternatively up to 96 GC area%. The purity of CETMS, when measured by the test methods described below and used in the examples, may be at least 72 GC area%, alternatively at least 81 GC area%, alternatively at least 86 GC area%, alternatively at least 89 GC area%, and alternatively at least 90 GC area%, while at the same time, the purity of CETMS may be up to 100 GC area%, alternatively up to 98 GC area%, alternatively up to 95 GC area%, alternatively up to 92 GC area%, and alternatively up to 90 GC area%. The amount of dimer may be at least 20 wt% (based on the combined weight of the alkoxysilane product and dimer), alternatively 20 wt% to 30 wt%, alternatively 20 wt% to 29 wt%, alternatively 20 wt% to 28 wt%, alternatively 20 wt% to 27 wt%, and alternatively 20 to 26 wt%. 【0029】 The reaction products generated as described above can be used in polyorganosiloxane compositions, such as room-temperature vulcanizable organopolysiloxane compositions. RTV organopolysiloxane compositions are known in the art and are disclosed, for example, in U.S. Patent No. 4,483,973 by Lucas et al., U.S. Patent No. 5,962,559 by Lucas et al., U.S. Patent No. 7,550,548 by Hatanaka et al., U.S. Patent No. 7,674,871 by Koch et al., U.S. Patent Publication No. 2007 / 0173597 by Williams et al., and PCT Patent Publication No. WO2007 / 024792. The reaction products, including CETMS and dimer, can function as adhesion promoters, coupling agents, and / or crosslinking agents in polyorganosiloxane compositions. Alternatively, the reaction products can be added to commercially available RTV sealants, such as XIAMETER® SLT-5200 from DSC. While not bound by theory, it is believed that polyorganosiloxane compositions containing reaction products prepared as described herein may exhibit superior adhesion to comparative polyorganosiloxane compositions that do not contain CETMS or contain CETMS with lower levels of dimers than those described herein. [Examples] 【0030】 These examples are intended to illustrate the present invention to those skilled in the art and should not be construed as limiting the inventions described in the claims. The materials used herein are listed in Table 1. 【0031】 [Table 1] 【0032】 Example 1 (Comparative Example) CETMS 1 was purchased from MPM. CETMS 1 contained 2% by weight of dimer, as measured by GC. 【0033】 Example 2 - Dow CETMS 2 (Comparison) Cyanoethyltrimethoxysilane (CETMS) was synthesized by the following method: 1514 g of cyanoethyltriethoxysilane (CETES) was placed in a 7 L glass reactor, and 3299 g of methanol was added while stirring. Then, 1.50 mL of 3 M HCl from the methanol was added to the reactor. The reaction was completed at room temperature after 1 hour. Next, under a vacuum of 75–150 mmHg, the reaction mixture was distilled while heating to 30–60°C to remove methanol and ethanol, and then fresh methanol was added. 【0034】 The partially reacted CETES recovered from distillation was then reacted in two cycles. 3265 g of methanol was added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol, after which fresh methanol was added. 【0035】 The partially reacted CETES recovered from distillation was then reacted in cycle 3. 3301 g of methanol was added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. Then, under a vacuum of 75-150 mmHg and heated to 30-60°C, the reaction mixture was distilled to remove methanol and ethanol, and fresh methanol was added. 【0036】 The partially reacted CETES recovered from distillation was then reacted in the fourth cycle. 3352 g of methanol was added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol. 【0037】 The final CETMS product recovered after distillation was then neutralized with 25% by weight sodium methoxide in methanol and subsequently filtered. 1047 g of the final CETMS product was recovered. The CETMS product was measured by GC to consist of 89.7% CETMS, 5.0% cyanoethyl dimethoxymonoethoxysilane (CE2M1ES), 0.1% cyanoethyl monomethoxydiethoxysilane (CE1M2ES), 1.1% methanol, and 4.0% dimer. 【0038】 Example 3 - Reaction product produced by the process described herein Cyanoethyltrimethoxysilane (CETMS) was synthesized by the following method: 1480 g of cyanoethyltriethoxysilane (CETES) was placed in a 7 L glass reactor, and 3271 g of methanol was added while stirring. Next, 7.3 g of deionized water was added to the reactor. Then, 2.0 mL of 3 M HCl in the methanol was added to the reactor. The reaction was completed at room temperature after 1 hour. The reaction mixture was then distilled under a vacuum of 75-150 mmHg while heating to 30-60°C to remove methanol and ethanol, and then fresh methanol was added. 【0039】 The partially reacted CETES recovered from distillation was then reacted in two cycles. 3244 g of methanol and 7.4 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75-150 mmHg while heating to 30-60°C to remove methanol and ethanol, after which fresh methanol was added. 【0040】 The partially reacted CETES recovered from distillation was then reacted in cycle 3. 3269 g of methanol and 7.75 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. Then, under a vacuum of 75-150 mmHg and heated to 30-60°C, the reaction mixture was distilled to remove methanol and ethanol, after which fresh methanol was added. 【0041】 The partially reacted CETES recovered from distillation was then reacted in the fourth cycle. 3289 g of methanol and 7.5 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol. 【0042】 The final CETMS product recovered after distillation was then neutralized with 25% by weight sodium methoxide in methanol and subsequently filtered. 1051 g of the final CETMS product was recovered. The CETMS product was measured by GC to consist of 76.1% CETMS, 3.6% cyanoethyl dimethoxymonoethoxysilane (CE2M1ES), 3.8% methanol, and 20.2% dimer. 【0043】 Example 4 - Reaction product produced by the process described herein Cyanoethyltrimethoxysilane (CETMS) was synthesized by the following method: 1441 g of cyanoethyltriethoxysilane (CETES) was placed in a 7 L glass reactor, and 3273 g of methanol was added while stirring. Next, 5.0 g of deionized water was added to the reactor. Then, 1.32 mL of 3 M HCl in the methanol was added to the reactor. The reaction was completed at room temperature after 1 hour. The reaction mixture was then distilled under a vacuum of 75-150 mmHg while heating to 30-60°C to remove methanol and ethanol, and then fresh methanol was added. 【0044】 The partially reacted CETES recovered from distillation was then reacted in two cycles. 3158 g of methanol and 5.5 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol, after which fresh methanol was added. 【0045】 The partially reacted CETES recovered from distillation was then reacted in cycle 3. 3307 g of methanol and 5.0 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. Then, under a vacuum of 75-150 mmHg and heated to 30-60°C, the reaction mixture was distilled to remove methanol and ethanol, after which fresh methanol was added. 【0046】 The partially reacted CETES recovered from distillation was then reacted in the fourth cycle. 3282 g of methanol and 5.0 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol, after which fresh methanol was added. 【0047】 The partially reacted CETES recovered from distillation was then reacted in the fifth cycle. 3282 g of methanol and 16.1 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol. 【0048】 The final CETMS product recovered after distillation was then neutralized with 25% by weight sodium methoxide in methanol and subsequently filtered. 1031 g of the final CETMS product was recovered. The CETMS product was measured by GC to consist of 71.4% CETMS, 2.3% cyanoethyl dimethoxymonoethoxysilane (CE2M1ES), 3.7% methanol, and 26.3% dimer. 【0049】 Example 5 - Reaction product produced by the process described herein Cyanoethyltrimethoxysilane (CETMS) was synthesized by the following method: 1595 g of cyanoethyltriethoxysilane (CETES) was placed in a 7 L glass reactor, and 3526 g of methanol was added while stirring. Next, 2.8 g of deionized water was added to the reactor. Then, 1.50 mL of 3 M HCl in the methanol was added to the reactor. The reaction was completed at room temperature after 1 hour. Next, under a vacuum of 75-150 mmHg, the reaction mixture was distilled while heating to 30-60°C to remove methanol and ethanol, and then fresh methanol was added. 【0050】 The partially reacted CETES recovered from distillation was then reacted in two cycles. 3594 g of methanol and 2.7 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol, after which fresh methanol was added. 【0051】 The partially reacted CETES recovered from distillation was then reacted in cycle 3. 3642 g of methanol and 2.8 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75-150 mmHg while heating to 30-60°C to remove methanol and ethanol, after which fresh methanol was added. 【0052】 The partially reacted CETES recovered from distillation was then reacted in the fourth cycle. 3601 g of methanol and 2.8 g of water were added to the reaction mixture. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then distilled under a vacuum of 75–150 mmHg while heating to 30–60°C to remove methanol and ethanol. 【0053】 The final CETMS product recovered after distillation was then neutralized with 25% by weight sodium methoxide in methanol and subsequently filtered. 1197 g of the final CETMS product was recovered. The CETMS product was measured by GC to consist of 85.4% CETMS, 4.0% cyanoethyl dimethoxymonoethoxysilane (CE2M1ES), 0.1% cyanoethyl monomethoxydiethoxysilane (CE1M2ES), 0.9% methanol, and 9.6% dimer. 【0054】 Reference example 6 In this reference example, the materials prepared as described above in Examples 1 to 4 were tested as adhesion promoters in a curable polyorganosiloxane composition (sealant). The adhesion peel test was performed as described below. The results are shown in Table 2 below. 【0055】 [Table 2] 【0056】 The results in Table 2 above show that using a reaction product containing 20% ​​to 26% by weight of dimer (the remaining CETMS based on the combined weight of CETMS and dimer) in a curable polyorganosiloxane composition improves adhesion compared to using the same composition but with less dimer (2% to 4% by weight) of CETMS. Specifically, after immersion in water, the adhesive peel strength (pli) was higher for specimens prepared using CETMS containing 20% ​​or 26% dimer compared to specimens containing 2% or 4% dimer. 【0057】 Test method The composition of the material was verified using gas chromatography (GC) with an internal standard composition of 1 wt% nonane in acetonitrile. All reported compositions are based on GC area percentages unless otherwise indicated. An Agilent 7890A GC system with helium carrier gas and FID detector was used with a Restek Rtx-1 30m × 0.25mm × 1um. The flow rate was set to a constant 1.5 mL / min. The gradient started at 40°C for 2 minutes, then increased to 260°C at a rate of 20°C / min. The final temperature of 260°C was held for 2 minutes. Other conditions were as follows: 1.1 μL injection volume 2. Needle cleaning with acetonitrile for solvent A and B washing. 3. Split / Splitless inlet temperature and FID temperature 260°C 4. Divided injection with a division ratio of 50:1 【0058】 Titration was performed using Metrohm Brinkmann 776 Dosimat, and the chloride level was determined using BCP indicator and 0.1N KOH. 【0059】 Adhesion peel tests were performed on anodized aluminum substrates according to a modified version of ASTM C794. The substrates were prepared by wiping twice with isopropyl alcohol (IPA) and air-drying. A stainless steel screen (20 × 20 × 0.016 inches) (50.8 × 50.8 × 0.0406 cm), 0.5 inches (1.27 cm) thick and wide, was cleaned with xylene and primed with DOWSIL® 1200 OS primer from Dow Silicones Corporation, with at least 24 hours of drying after each step. A bead of sealant was applied to the substrate and stretched to a thickness of 1 / 8 inch (0.3175 cm). The screen was then lightly pressed into the sealant, applying a second bead of sealant onto the screen and drawing down to a total thickness of 1 / 4 inch (0.635 cm). The test specimens were adjusted at room temperature and 50% relative humidity (RH) for 7 hours. Before testing, a new score mark was made with a knife at the substrate / sealant interface directly below the screen. Adhesive peel strength (pli) was measured using an Instron 33R 4465 with a 5kN load cell by pulling the screen 180° at 2.0 inches / min (5.08 cm / min). After peeling, user evaluation of the failure mode (adhesive failure vs. cohesive failure) was performed and recorded. After measuring the initial peel strength, the same cured peel preparation was aged in water for 1 day and retested, followed by a final test after immersion in water for a further 6 days. [Industrial applicability] 【0060】 To achieve a high conversion rate for the conversion of CETES to CETMS via the transesterification reaction of CETES and MeOH, the reaction and subsequent removal of EtOH and other materials may be repeated several times. Due to thermodynamic equilibrium limitations and the higher volatility of MeOH compared to EtOH, the reverse reaction may occur during the removal of EtOH (e.g., via stripping and / or distillation) via the reaction of CETMS (when x=0 in the above reaction scheme) or a partially methoxylated species (when x=1 or 2) with an EtOH byproduct (which cannot be removed until the lower boiling point MeOH reactants are removed first). 【0061】 The inventors have surprisingly discovered that by adding water to CETMS to generate a dimer, a reaction product (composition) is obtained that improves the adhesion of the cured product of a polyorganosiloxane composition compared to the adhesion of the cured product of a polyorganosiloxane composition containing CETMS with a smaller amount of dimer. 【0062】 Definitions and Usage of Terms The total amount of all starting materials in the composition is 100% by weight. The summary and abstract of the invention are incorporated herein by reference. The articles “a,” “an,” and “the” each refer to one or more unless specifically indicated by the context of the specification. The singular form includes the plural form unless otherwise stated. Each embodiment or alternative presented herein may be combined with any other embodiment or alternative. The term “comprising” and its derivatives, e.g., “comprise” and “comprises,” mean “including,” “include,” “consisting essentially of,” and “consisting of,” and are used herein in their broadest sense to encompass these views. The use of “for example,” “eg,” “such as,” and “including” to list examples is not limited to the examples listed. Therefore, "for example" or "etc." means "for example, but not limited to these" or "etc., but not limited to these," and includes other similar or equivalent examples. 【0063】 The appended claims are not limited to the obvious and specific compounds, compositions, or methods described in the embodiments for carrying out the invention, and it should be understood that these may differ between the specific embodiments that fall within the scope of the appended claims. With respect to any group of Markush elements relied upon herein to illustrate specific features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each element of each group of Markush elements, independent of all other Markush elements. Each element of a group of Markush elements may be relied upon individually and / or in combination to provide sufficient support for specific embodiments within the scope of the appended claims. 【0064】 The abbreviations used in this application are defined in Table 5 below. 【0065】 [Table 3]

Claims

[Claim 1] A process for preparing a reaction product comprising an alkoxysilane product and a dimer, wherein the process is: １） (A) Cyanoethyltriethoxysilane, (B) Stoichiometric excess amount of methanol, (C) Water, and (D) Combining starting materials containing an acid catalyst, thereby generating a reaction mixture, Optionally, 2) Add to the reaction mixture, (D1) bituminous activated carbon; (D2) Coconut activated carbon having an iodine value of at least 1200 mg / g, and (D3) Both (D1) and (D2) Adding (E) activated carbon selected from the group consisting of, 3) Removing the material containing methanol, ethanol, and the acid catalyst from the reaction mixture, 4) A process comprising repeating steps 1) to 3) once or more times, thereby forming the reaction product. [Claim 2] The process according to claim 1, wherein in step 1), a certain amount of (A) cyanoethyltriethoxysilane and a certain amount of (B) methanol are used in a molar ratio (B):(A) of at least 5:1, alternatively 5:1 to 30:1, alternatively >5:1 to 30:1, or alternatively 15:1 to 30:

1. [Claim 3] (D) The process according to claim 1 or claim 2, wherein the acid catalyst is selected from the group consisting of HCl and ion exchange resins. [Claim 4] (D) The process according to any one of claims 1 to 3, wherein the acid catalyst is HCl, and the HCl is used in an amount of at least 30 ppm based on the sum of the weight of (A) the cyanoethyltriethoxysilane and (B) the methanol, and the duration of step 3) is 1 to 4 hours. [Claim 5] The process according to any one of claims 1 to 4, wherein in step 1), the amount of water is 0.05% by weight to 1% by weight based on (B) the weight of methanol. [Claim 6] The process according to any one of claims 1 to 5, wherein step 2) is included. [Claim 7] The reaction product is Formula for a maximum of 80% by weight 【Chemistry 1】 The alkoxysilane product and Formula for at least 20% by weight 【Chemistry 2】 The process according to any one of claims 1 to 6, comprising a dimer of (wherein each R is independently selected from the group consisting of methyl and ethyl, and each subscript x is independently 0 to 2). [Claim 8] The process according to claim 7, wherein each R is methyl and the subscript x = 0. [Claim 9] The process according to claim 7 or 8, wherein the composition comprises 80% to 70% by weight of the alkoxysilane product and 20% to 30% by weight of the dimer. [Claim 10] Use of the reaction product prepared by the process described in any one of claims 1 to 9 in a polyorganosiloxane sealant composition. [Claim 11] The use according to claim 10, wherein the composition is an adhesion promoter, a coupling agent, or a crosslinking agent. [Claim 12] A method comprising adding the reaction product described in any one of claims 1 to 9 to a polyorganosiloxane sealant composition. [Claim 13] The method according to claim 12, wherein the polyorganosiloxane sealant composition comprises an alkoxy-functional polyorganosiloxane. [Claim 14] The method according to claim 12, wherein the polyorganosiloxane sealant composition comprises an acyloxy-functionalized polyorganosiloxane.