Method for preparing poly(diorgano / organohydrogen)siloxane copolymers

Abstract

A method for preparing poly(diorgano / organohydrogen)siloxane copolymers is provided that involves the use of vibrational spectroscopy techniques.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application asserts the interests of U.S. Provisional Patent Application No. 63 / 125,015, filed December 14, 2020, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 125,015 is incorporated herein by reference.

[0002] (Field of Invention) A method for preparing poly(diorgano / organohydrogen)siloxane copolymers is disclosed. More specifically, the method is based on the formula HRSiO 2 / 2 [In the formula, each R is a monovalent hydrocarbyl group or a halogenated hydrocarbyl group](D H This method produces copolymers having a desired chain distribution of units.

[0003] Introduction U.S. Patent No. 8,686,175 discloses a method for producing siloxanes. This method involves reacting at least two siloxanes at an ambient temperature of ~110°C in the presence of an ion exchange resin catalyst containing 6 to 19% by weight of water based on the dry weight of the ion exchange resin catalyst. Also disclosed is a method for reusing an ion exchange resin catalyst after reacting at least two siloxanes in the presence of the ion exchange resin catalyst, which involves adding water to the ion exchange resin catalyst to readjust the water content to 6 to 19% by weight of water based on the dry weight of the catalyst, and then reacting at least two siloxanes in the presence of the ion exchange resin catalyst with the readjusted water content.

[0004] NMR has been used to identify polyorganohydrogensiloxanes, but real-time analysis of reaction mixtures for producing polyorganohydrogensiloxanes on a commercial scale is difficult, expensive, and impractical using NMR technology. Therefore, conventional processes can have the disadvantage of low productivity, as it is sometimes desirable to stop the reaction when or immediately after reaching the desired polyorganohydrogensiloxane product structure in order to minimize processing time. However, the time to reach the desired product structure can vary from batch to batch for various reasons, including variations in process conditions such as the specific siloxane selected as a reactant and the selected temperature. As a result, the time required to obtain the desired product varies from batch to batch. [Overview of the project]

[0005] A method for preparing poly(diorgano / organohydrogen)siloxane copolymers is provided herein. 1) A) Formula (R2SiO 2 / 2 ) Source of siloxane units, B) Formula (RHSiO 2 / 2 ) Source of siloxane units, [In the formula, each R is independently selected from the group consisting of monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups], and C) acid catalyst; By combining starting materials containing, a mixture is formed, 2) By stirring the mixture at a temperature of 20°C to 110°C, a reaction mixture containing poly(diorgano / organohydrogen)siloxane copolymer is formed via an equilibration reaction, 3) Using vibrational spectroscopy techniques selected from the group consisting of infrared spectroscopy and Raman spectroscopy, decoupling (RHSiO) in the reaction mixture. 2 / 2 ) concentration and coupling (RHSiO 2 / 2 Monitoring the spectral region that includes the absorbance band corresponding to one or both of the concentrations in units, 4) The equilibration reaction is stopped when the target value related to the absorbance band is reached. [Brief explanation of the drawing]

[0006] [Figure 1] The following IR spectra show the positions of the decoupling and coupling (RHSiO2 / 2) absorption bands (SiH peaks) measured in Example 1. The dashed vertical line indicates the baseline point. The solid vertical line indicates the peak center. [Figure 2] The decoupling SiH peak area as a function of reaction time, as measured by IR in Example 1, is shown. [Figure 3] The decoupling SiH peak height as a function of reaction time, as measured by IR in Example 1, is shown. [Figure 4] The coupling SiH peak area as a function of reaction time, as measured by IR in Example 1, is shown. [Figure 5] The coupling SiH peak height as a function of reaction time, as measured by IR in Example 1, is shown. [Figure 6] The Raman spectra showing the locations of the decoupling and coupling SiH peaks measured in Example 1 are shown. The dashed vertical line indicates the baseline point. The solid vertical line indicates the peak center. [Figure 7] The decoupling SiH peak area as a function of reaction time, measured by Raman spectroscopy in Example 1, is shown. [Figure 8] The decoupling SiH peak height as a function of reaction time, as measured by Raman spectroscopy in Example 1, is shown. [Figure 9] The coupling SiH peak area as a function of reaction time, measured by Raman spectroscopy in Example 1, is shown. [Figure 10] The coupling SiH peak height as a function of reaction time, as measured by Raman spectroscopy in Example 1, is shown. [Figure 11]Shows the decoupling SiH peak area as a function of reaction time, measured by IR in Example 2. [Figure 12] Shows the decoupling SiH peak area as a function of reaction time, measured by IR in Example 3. [Figure 13] Shows the decoupling SiH peak area as a function of reaction time, measured by IR in Example 4. [Figure 14] Shows the decoupling SiH peak area as a function of reaction time, measured by IR in Example 5.

Mode for Carrying Out the Invention

[0007] Step 1) of the method described above in the "Summary of the Invention" involves forming a mixture by combining a starting material comprising A) a source of siloxane units of the formula (R2SiO 2 / 2 ), B) a source of siloxane units of the formula (RHSiO 2 / 2 ) [where each R is independently selected from the group consisting of monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups], and C) an acid catalyst.

[0008] Starting materials A) and B) can be one or more polyorganosiloxanes. The polyorganosiloxane has the unit formula: (R3SiO 1 / 2 ) t (R2HSiO 1 / 2 ) u (R2SiO 2 / 2 ) v (RHSiO 2 / 2 ) w (RSiO 3 / 2 ) x (HSiO 3 / 2 ) y (SiO 4 / 2 ) z[In the formula, the subscripts t, u, v, w, x, y, and z represent the quantities of each unit, where t≧0, u≧0, v≧1, w≧1, x≧0, y≧0, and z≧0, where the quantity (v+w)≧3, and the quantity (x+y+z) ranges from 0 to a value sufficient to provide up to 20 mol% of siloxane units in the molecule, and the quantity (t+u+v+w)≧3]. Alternatively, (t+u+v+w) can have values ​​of 3 or greater, or 3 to 2,000, or 3 to 1,000, or 3 to 500, or 3 to 300, or 3 to 200. In this unit formula, each R is independently selected from the group consisting of monovalent hydrocarbyl groups and monovalent halide hydrocarbyl groups. Alternatively, when the polyorganosiloxane is linear or cyclic, the quantity (x+y+z)=0.

[0009] Suitable monovalent hydrocarbyl groups for R are exemplified by alkyl, alkenyl, and aryl groups. Alkyl groups for R may include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, t-butyl, sec-butyl, and / or isobutyl), pentyl (including cyclopentyl, n-pentyl, and branched isomers having 5 carbon atoms), hexyl (including cyclohexyl, n-hexyl, and branched isomers having 6 carbon atoms), heptyl (including cycloheptyl, n-heptyl, and branched isomers having 7 carbon atoms), octyl (including cyclooctyl, n-octyl, and branched isomers having 8 carbon atoms), nonyl (including cyclononyl, n-nonyl, and branched isomers having 9 carbon atoms), and decyl (including cyclodecyl, n-decyl, and branched isomers having 10 carbon atoms). Suitable alkenyl groups for R can be selected from vinyl, allyl, and hexenyl; or vinyl and hexenyl; or vinyl. Suitable aryl groups for R are exemplified by, but are not limited to, cyclopentadienyl, phenyl, anthracenyl, naphthyl, tolyl, xylyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl. Suitable monovalent hydrocarbyl groups for R are monovalent hydrocarbyl groups (such as those listed above) in which one or more hydrogen atoms bonded to a carbon atom are formally substituted with halogen atoms. Examples of halogenated hydrocarbon groups include haloalkyl groups and haloalkenyl groups.Examples of haloalkyl groups include trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, as well as chlorinated alkyl groups such as chloromethyl, 3-chloropropyl, 2,2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl. Examples of haloalkenyl groups include chloroallyl groups. Alternatively, each R may be a monovalent hydrocarbyl group. Alternatively, each R may be an alkyl group. Alternatively, each R can be selected from methyl, ethyl, propyl, or butyl. Or it can be methyl, ethyl, or methyl.

[0010] Polyorganosiloxanes are (R2SiO 2 / 2 ) units and (RHSiO 2 / 2 When both units are present, starting materials A) and B) may be the same molecule. Alternatively, starting materials A) and B) may be different molecules.

[0011] For example, starting material A) is A1) unit formula (R2SiO 2 / 2 ) c [In the formula, 3 ≤ c ≤ 12] Cyclic polydiorganosiloxane, A2) Unit formula (R3SiO 1 / 2 ) a (R2HSiO 1 / 2 ) d (R2SiO 2 / 2 ) bLinear polyorganosiloxanes containing [a + d = 2 and b ≤ 200] in the formula; and can be selected from the group consisting of combinations of both A1) and A2). In the unit formulas of A1) and A2), each R is as described above. Alternatively, each R may be an independently selected monovalent hydrocarbyl group, an alkyl group, or a methyl group. Alternatively, in starting material A1), the subscript c may be 3 or greater, or 3 ≤ c ≤ 9, or 3 ≤ c ≤ 6, or 4 ≤ c ≤ 6. Alternatively, in starting material A2), the subscript d may be 0. Cyclic polydiorganosiloxanes suitable for use as starting material A1) are known in the art and are commercially available. For example, phenylmethylcyclosiloxanes and dimethylcyclosiloxanes, exemplified by octa-aruganocyclotetrasiloxanes such as 2,2,4,4,6,6,8,8,-octamethylcyclotetrasiloxane; decaorganocyclopentasiloxanes such as 2,2,4,4,6,6,8,8,-decamethylcyclopentasiloxane; and dodecaorganocyclohexasiloxanes such as 2,2,4,4,6,6,8,8,10,10-dodecamethylcyclohexasiloxane are known in the art and are commercially available from various suppliers such as Dow Silicones Corporation (Midland, Michigan, USA), Gelest, Inc. (Morrisville, Pennsylvania, USA), and Sigma-Aldrich, Inc. (St. Louis, Missouri, USA). Suitable linear polyorganosiloxanes for use as starting material A2) include trimethylsiloxy-terminated polydimethylsiloxanes, which are also known in the art and commercially available from the same suppliers as described above. For example, trimethylsiloxy-terminated polydimethylsiloxanes with viscosities of 5 cSt, 10 cSt, 50 cSt, 500 cSt, and 1,000 cSt are commercially available from Dow Silicones Corporation (Midland, Michigan, USA). Viscosity can be measured at 25°C and 0.1–50 RPM using a Brookfield DV-III cone and plate viscometer with a #CP-52 spindle.Those skilled in the art will recognize that the rotational speed decreases as viscosity increases and can select an appropriate rotational speed when measuring viscosity using this test method. Alternatively, suitable dimethylhydrogensiloxy-terminated polydimethylsiloxanes can be used as starting material A2), which are also known in the art and are commercially available from various distributors, including Gelest, Inc., under trade names: DMS-HM15, DMS-H03, DMS-H25, DMS-H31, and DMS-H41. Alternatively, starting material A) may be one that does not contain silicon-bonded hydrogen atoms.

[0012] Starting material B) is B1) unit formula (HRSiO 2 / 2 ) c Cyclic polyorganohydrogensiloxane [wherein 3≦c≦12], unit formula (R3SiO2) 1 / 2 ) a (R2HSiO 1 / 2 ) d (RHSiO 2 / 2 ) eA linear polyorganohydrogensiloxane [wherein the formula (a+d)=2 and 3≦e≦200] may be selected from the group consisting of combinations of both B1) and B2). In the unit formulas of B1) and B2), each R is as described above. Alternatively, in starting material B), each R may be an independently selected monovalent hydrocarbyl group, an alkyl group, or a methyl group. Alternatively, in the unit formula of B1), the subscript c may be 3 or greater, or 3≦c is ≦9, or 3≦c is ≦6, or 4≦c is ≦6. Alternatively, in the unit formula of B2), the subscript d may be 0. Organohydrogencyclosiloxanes suitable for starting material B1) are known in the art and are commercially available. For example, organohydrogencyclosiloxanes such as 2,4,6,8-tetramethyl-2,4,6,8-tetrahydrocyclotetrasiloxane; organohydrogencyclopentasiloxanes such as 2,4,6,8,10-pentamethyl-2,4,6,8,10-tetrahydrocyclopentasiloxane; and organohydrogencyclohexasiloxanes such as 2,4,6,8,10,12-hexamethyl-2,4,6,8,10,12-tetrahydrocyclohexasiloxane are known in the art and are commercially available from various suppliers such as Dow Silicones Corporation and Gelest, Inc. Alternatively, linear polyorganohydrogensiloxanes suitable for starting material B2) are also known in the art, commercially available, or can be produced by known methods. For example, bis-trimethylsiloxy-terminated polymethylhydrogensiloxane homopolymers and bis-trimethylsiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers, bis-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane homopolymers and bis-dimethylhydrogensiloxy-terminated poly(dimethyl / methylhydrogen)siloxane copolymers may be used.Suitable polyorganohydrogensiloxanes are also commercially available, for example, from Gelest, Inc. under the trademark names: HMS-H271, HMS-071, HMS-993, HMS-301, HMS-301 R, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301, HPM-502, and HMS-HM271. Methods for preparing linear polyorganohydrogensiloxanes, such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in U.S. Patents 2,823,218, 5,310,843, 4,370,358, 4,707,531, and 4,329,273 by Speier et al.

[0013] Starting material C) is a catalyst suitable for catalyzing the equilibration reaction in the method described herein. The catalyst may be homogeneous or heterogeneous. Suitable homogeneous catalysts include sulfonic acids such as toluenesulfonic acid and trifluoromethanesulfonic acid (triflic acid). Suitable heterogeneous catalysts include acid-activated bleached earth (bentonite, montmorillonite, or Fuller's earth), acidic clays such as Tonsyl clay and Filtrol® acidic clay, which are commercially available from Sigma-Aldrich, Inc., and ion exchange resins such as sulfonated macrocrosslinked cation exchange resins. Various ion exchange resins are known in the art and are commercially available, for example, from DuPont de Nemours, Inc. (Wilmington, Delaware, USA) under the trade name AMBERLYST®. Suitable catalysts for use as starting material C) are known in the art, for example, acid catalysts disclosed in U.S. Patents 2,823,218, 5,310,843, 4,370,358, 4,707,531, and 4,329,273 by Speier et al. Alternatively, the catalyst may be a heterogeneous catalyst. Heterogeneous catalysts are exemplified, for example, by those disclosed in U.S. Patents 8,686,175 and 8,722,834 by Gehrig et al.

[0014] The amount of the catalyst (starting material C) is sufficient to catalyze the equilibration reaction. The exact amount of catalyst C) varies depending on various factors such as whether the catalyst is homogeneous or heterogeneous, and whether the method is carried out in batch or continuous order. However, the amount of catalyst may be greater than 0 to 10% by weight, or greater than 0 to 5% by weight, based on the total weight of the starting materials A), B), C), D), and E) used in the method. Alternatively, the amount of heterogeneous catalyst used in a batch process may be greater than 0 to 5% by weight, greater than 0 to 2% by weight, or 0.5% to 5% by weight, or 1% to 5% by weight, or 1% to 2% by weight, based on the total weight of the starting materials A), B), C), D), and E) used in step 1) of the method. Alternatively, when the method is carried out in batch order using a homogeneous catalyst, the amount of catalyst may be greater than 0 to 1%. Alternatively, when the method is carried out continuously, the amount of catalyst may vary. For example, heterogeneous catalysts can be used in packed beds for continuous processes, and the amount of catalyst varies depending on the size of the reactor.

[0015] The starting materials used in this method may optionally include one or more additional starting materials. For example, the additional starting materials may be selected from the group consisting of D) water, E) end-sealing agents, or both. Water may optionally be added to the starting materials used in this method to improve the reactivity of the catalyst. For example, when the catalyst is an ion exchange resin provided in a dry form, or an ion exchange resin reused from one batch to another, water can be added to reactivate the catalyst. The amount of water may vary, but may be as described in U.S. Patent No. 8,686,175.

[0016] Unlike starting materials A) and B), the end-sector agent has the unit formula (R3SiO 1 / 2 ) e (R2HSiO 1 / 2 ) f (R2SiO 2 / 2 ) g (RHSiO 2 / 2 ) h[wherein R is as described above, the subscript e is 0, 1, or 2, the subscript f is 0, 1, or 2, the quantity (e+f)=2, the subscript g≧0, the subscript h≧0, and 0≦(g+h)≦3] may have this. Alternatively, the quantity (g+h) may be 0~2 or 0~1. End-chain agents are known in the art and are commercially available. Examples include 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,5,5,5-octamethyltrisiloxane, both of which are available from Sigma-Aldrich, Inc. and / or other suppliers such as Dow Silicones Corporation or Gelest, Inc. The end-chain agent is optional and may be used in amounts of 0-44.5% by weight, 0-40% by weight, 0-30% by weight, or 0-25% by weight, based on the total weight of the starting materials A), B), C), D), and E). The remainder of the starting materials used in this method may be starting materials A) and B). Alternatively, starting materials A) and B) may constitute 45.5% to less than 100% by weight, 50% to less than 100% by weight, 60% to less than 100% by weight, or 75% to less than 100% by weight, based on the total weight of the starting materials A), B), C), D), and E) used in this method.

[0017] Steps 1) and 2) of this method can be carried out by any convenient means using conventional equipment. For example, the starting materials can be combined in a jacketed container equipped with a stirrer. The starting materials can be added to the container in any order. Steps 1) and 2) can be carried out sequentially or in parallel. Step 2) can be carried out by mixing with a stirrer while controlling the temperature inside the container to 20°C to 110°C or 23°C to 80°C when the equilibrium reaction occurs.

[0018] The equilibration reactions described herein are illustrated by the following exemplary reaction scheme:

[0019] [ka] [In the formula, R is as described above, the subscript m is 1 to 10, the subscript n is 3 to 200, the subscript o is 0 to 3, the amount (p+q) ≥ 3, mainly 3 to 9, and the amount (r+s) = 10 to 300]. Alternatively, the subscript s may be 30 to 250, and the subscript r may be 3 to 70. Alternatively, each R may be methyl, the subscript m may have an average value of 2, the subscript n may have an average value of 70, or 60 to 70, and the subscript o may be 0. The above reaction scheme involves the equilibration of the ≡Si-O-Si≡ bond from one molecule to another, including ring opening of the cyclic siloxane and end sealing with the end-sealing agent shown above. It may be desirable to produce a fully equilibrated product.

[0020] Using the above reaction scheme, in step 2), a poly(diorgano / organohydrogen)siloxane copolymer product and a mixed cyclic by-product are formed. The copolymer is of the formula (R2SiO 2 / 2 The D unit of ) and the formula (RHSiO 2 / 2 ) D H It includes units. Although not bound by theory, during step 2), the copolymer, once formed, has a blocky distribution of bifunctional units, i.e., D H It is thought to have blocks of units and blocks of D units. As the equilibrium reaction progresses over time, D units and D H The position of the units changes to a more randomized chain in the main chain of the copolymer. Using vibrational spectroscopy techniques, coupling D H Units and decoupling D H The absorption band (peak on the spectrum) corresponding to the unit can be determined. Coupling refers to the formation of another D in the copolymer backbone. H D adjacent to the unit H It refers to a unit. Decoupling is another D in the copolymer backbone. H D not adjacent to the unit H It refers to a unit.

[0021] The inventors have found that the reaction mixture in step 3) of the above method can be monitored in real time using vibrational spectroscopy techniques, such as infrared (IR) spectroscopy or Raman spectroscopy. Furthermore, the reaction mixture can be monitored in situ using vibrational spectroscopy techniques. In the past, IR and Raman spectroscopy have been used to measure the concentration of substituents present in polyorganohydrogensiloxane (e.g., which substituents are bonded to silicon atoms and in what amounts), but these vibrational spectroscopy techniques have not been used to measure the chain of siloxane units in the copolymer backbone (e.g., D units and D units). H It has not been used to detect the chain of units. Surprisingly, the inventors have found that vibrational spectroscopy techniques can detect D units and D in the copolymer back chain. H We found that it is possible to detect changes in the chain of units (e.g., block chain or random chain). Furthermore, the vibrational spectroscopy techniques described herein are D:D H It can be used for copolymers with a ratio of at least 1:1, or at least 1.5:1, or at least 2:1. At the same time, the D:D ratio of the copolymer H The ratio may be up to 30:1, or up to 15:1, or up to 10:1, or up to 5:1, or up to 3:1. Alternatively, the vibrational spectroscopy techniques described herein may be D:D H It can be used for copolymers with ratios of 1:1 to 30:1, or 1:1.5 to 1:2.5, or 1:2 to 1:3. Alternatively, the vibrational spectroscopy techniques described herein can be used for D:D copolymers. H It can be used in copolymers with ratios of 100:1 to 1:100, or 75:1 to 1:75, or 50:1 to 1:50, or 30:1 to 1:30, or 5:1 to 1:5, or 3:1 to 1:3, or 2.5:1 to 1:2.5, or 2.1 to 1:2, or 1:1.5:1 to 1:1.5.

[0022] The intensity of the absorbance band (i.e., the peak height and / or peak area on the spectrum measured by vibrational spectroscopy) can be measured at time intervals as the equilibration reaction progresses. The peak area and peak height of the decoupling SiH absorbance band increase with increasing reaction time, while the peak area and peak height of the coupling SiH absorbance band decrease with increasing reaction time. U.S. Patent Application Publication 2004 / 0198927 discloses an apparatus for measuring the intensity of the absorbance band (to obtain peak height and peak area) using vibrational spectroscopy. These absorbance band characteristics can be used to set target values ​​for reaction termination, optimize the properties of the poly(diorgano / organohydrogen)siloxane copolymer, and / or optimize the reaction batch time. Target values ​​can be set based on the decoupling SiH peak area, decoupling SiH peak height, coupling SiH peak area, and / or coupling SiH peak height. The reaction can be controlled by terminating the reaction when one or more of these characteristics reach the target value. Those skilled in the art can set target values ​​for each of these parameters to optimize application performance while minimizing batch time. Alternatively, target values ​​can be set based on the rate of change of any of these parameters. For example, as the reaction progresses, the decoupling SiH peak area increases to a maximum value and then levels off, as shown in Figure 2 below.

[0023] The rate of change in intensity of each absorbance band can be calculated over each time interval. When the rate of change approaches zero, this indicates that the copolymer has been completely equilibrated (in D units and D H(Units are randomly distributed). Therefore, if a random copolymer is desired, the target value may be set to, for example, 0% to 10% of the maximum absolute rate of change over a selected time interval, e.g., a 15-minute average value measurable during the equilibration reaction to stop the reaction in step 4). Alternatively, the target value may be set to stop the reaction when the rate of change reaches a predetermined value for any of the features of decoupling SiH peak area, decoupling SiH peak height, coupling SiH peak area, or coupling SiH peak height, as described and illustrated below in the examples of this specification. Alternatively, the target value may be set to stop the reaction when the decoupling SiH peak height or decoupling SiH peak area reaches its maximum value, or 90% to 100% of its maximum value. Alternatively, the target value may be set to stop the reaction when the coupling SiH peak height or coupling SiH peak area reaches its minimum value, or 0% to 10% of its minimum value. One or more features described herein can be used to set the target value and / or to determine when the target value has been reached. Alternatively, the resulting data can be smoothed using mathematical transformations to peak height, peak area, or rate of change data. This includes, but is not limited to, averaging across multiple instrument readings or fitting the data to a mathematical equation (such as exponential decay or a logistic function). Quantitative chemical analyses such as classical least squares (CLS), partial least squares (PLS), and principal component regression (PCR) can also be used instead of the univariate analyses described above to set target values.

[0024] The reaction in step 4) can be stopped by any convenient means, such as removing the catalyst by cooling and / or filtration (if a heterogeneous catalyst is used) or by neutralizing with a quenching agent to form a salt (if a homogeneous catalyst is used) and then removing it by filtration in batch or continuous manner.

[0025] The methods described herein may optionally further include one or more additional steps. For example, the method may further include step 5): recovering the poly(diorgano / organohydrogen)siloxane copolymer. During the equilibration reaction, by-products (e.g., the mixed ring described above in the exemplary reaction scheme) may be formed, and / or unreacted starting materials A) and / or B) may be present in the reaction mixture. Recovery can be carried out by any convenient means, for example, stripping and / or distillation to remove unreacted starting materials and / or by-products from the poly(diorgano / organohydrogen)siloxane copolymer.

[0026] The method may optionally further include a step 6) in which the steps 1) to 4) (and optionally 5) are repeated, while reusing the catalyst (if a heterogeneous catalyst is used) in step 1). Heterogeneous catalysts may require reactivation, and if the catalyst contains an ion exchange resin, the method may further include reactivating the catalyst by a technique that includes adding water to the catalyst before step 6), as described in U.S. Patent No. 8,686,175.

[0027] The methods described herein are based on the unit formula: (R3SiO 1 / 2 ) tt (R2HSiO 1 / 2 ) uu (R2SiO 2 / 2 ) vv (RHSiO 2 / 2 ) ww (RSiO 3 / 2 ) xx (HSiO 3 / 2 ) yy (SiO 4 / 2 ) zz[where the subscripted letters tt, uu, vv, ww, xx, yy, and zz represent the amounts of each unit in the copolymer, with subscripted letters tt ≥ 0, uu ≥ 0, vv ≥ 1, ww ≥ 1, xx ≥ 0, yy ≥ 0, zz ≥ 0, provided that the amount (vv + ww) ≥ 3, and the amount (xx + yy + zz) ranges from 0 to a value sufficient to provide up to 20 mol% of siloxane units in the copolymer molecules, and the amount (tt + uu + vv + ww) ≥ 3]. A poly(diorgano / organohydrogen)siloxane copolymer can be produced. Alternatively, the amount (tt + uu + vv + ww) can be 5 or more. Alternatively, (tt + uu + vv + ww) can have values of 5 to 2,000; or 5 to 1,000; or 10 to 500; or 25 to 300, or 50 to 200. This copolymer has at least one property, such as molecular weight, the distribution of (R2SiO 2 / 2 ) and (RHSiO 2 / 2 ) units, and the molar ratio (D:D H ratio) of the units of formula (R2SiO 2 / 2 ) to the units of formula (RHSiO 2 / 2 ) that is different from the starting materials (A) and (B). The copolymer also contains both D units and D H units. The D:D H ratio can be 100:! to 1:100; or 75:1 to 1:75; or 50:1 to 1:50; or 30:1 to 1:30; or 5:1 to 1:5, or 3:1 to 1:3, or 2.5:1 to 1:2.5; or 2:1 to 1:2, or 1.5:1 to 1:1.5; or 1:1 to 30:1, or 1:1.5 to 1:2.5, or 1:2 to 1:3. Alternatively, the copolymer produced by the method described herein can be linear, and when the subscripted letters xx = 0, yy = 0, and zz = 0, the copolymer has the unit formula: (R3SiO 1 / 2 ) tt [[ID=1】](R2HSiO 1 / 2 ) uu (R2SiO 2 / 2 ) vv (RHSiO 2 / 2 ) wwIt may have, the subscript tt is 0, 1, or 2, the subscript ww is 0, 1, or 2, the quantity (tt+uu)=2, the subscript vv>1, the subscript ww>1, and the subscripts vv and ww are D:D H The ratio has a value such that it is as described above. [Examples]

[0028] The following examples are intended to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as described in the claims. The reactants and other starting materials used in the examples are shown in Table 1 below. Where used in the following examples, “calculated value” refers to the D:D' and DP of the copolymer calculated based on the amount of each starting material used.

[0029] [Table 1]

[0030] In Table 1, DSC refers to Dow Silicones Corporation (Midland, Michigan, USA), and TDCC refers to The Dow Chemical Company (Midland, Michigan, USA).

[0031] Reference Example A - Infrared Spectroscopy Technology The reaction progress was monitored using a Mettler Toledo ReactIR 15 with the following configuration: MCT detector, SiComp (silicon) probe connected via AgX 9.5 mm × 1.5 m fiber (silver halide); sampling from 2800 to 650 with 4 wavenumber resolution; scan option: auto-selection; gain: 1x; HappGenzel apodization. Spectra were collected at 1-minute intervals for 12 hours.

[0032] Reference Example: B-Raman Spectroscopy Technique The progress of the reaction was monitored by Raman spectroscopy using the following apparatus and settings: i-Raman Prime Model BWS475-785-HT Custom probe: BAC101-CUST Details: High Throughput Industrial Raman Immersion Probe (BAC101), 0.5 inch O.D. × 10 inch L Hastelloy C-276 shaft and gold-sealed sapphire lens, and 785 nm excitation. 150 cm -1 Raman cut-off at. Laser fiber 105 μm core FC / PC termination. Raman fiber 300 μm core FC / PC termination. Fiber cable length 1.5 m. A processed mesh screen (100 × 100 mesh, wire diameter 0.0045 inch) was used and fitted onto the Raman probe to prevent solid-phase catalyst particles from entering the focal volume of the immersion optical system and excessive fluorescence.

[0033] Reference Example C - Curing time measurement (TC90). The curing rate of the elastomer formulation was measured using a Moving Die Rheometer (Monsanto Rheometer, MDR 2000, serial number 36A1D688). The elastomer formulation (5 ± 0.1 g) was placed between two Mylars and measured at 120 °C. The curing rate TC90 is a measure of the time required for 90% curing and is determined by the time it takes to reach 90% of the maximum torque for a given material / measurement.

[0034] In this Example 1, hexamethyldisiloxane (367.01 g), MeHsiloxane (596.66 g), and D4 cyclic compound (709.71 g) were packed into a 2 L jacketed reactor equipped with an inclined blade impeller and baffles. The reactor head was sealed, and the headspace was purged with N2 to obtain an inert atmosphere. The reaction temperature was controlled to 60°C by turning on the water flow to the water condenser, setting the stirrer to 600 RPM, and circulating the heat transfer fluid through the reactor jacket. Once the reaction temperature was reached, 8.96 g of catalyst was added to the reactor. IR spectra were collected in situ throughout the reaction using a Mettler Toledo React IR 15. Raman spectra were also collected in situ during the reaction using a B&W Tek i-Raman Pro system with Kaiser immersion optics. After the reaction was carried out for 11.5 hours, heating was stopped and the contents of the reactor were cooled to ambient temperature. At the end of the reaction, the obtained poly(dimethyl / methylhydrogen)siloxane copolymer had a D:D' ratio of 1:1 and a DP (calculated value) of 10.

[0035] Figure 1 below shows the IR spectrum collected during the reaction in Example 1. The peak area and peak height of the IR absorbance band of decoupling SiH increase with increasing reaction time, while the peak area and peak height of the IR absorbance band of coupling SiH decrease with increasing reaction time. These characteristics can be used to set target values ​​for reaction termination, optimize the physical properties of the copolymer, and optimize the reaction batch time. Target values ​​can be set based on the IR peak area of ​​decoupling SiH, the IR peak height of decoupling SiH, the IR peak area of ​​coupling SiH, the IR peak height of coupling SiH, or a combination of two or more of these. The reaction can be controlled by stopping the reaction when any of these characteristics reach a predetermined target value. Those skilled in the art can set target values ​​for each of these parameters to optimize application performance while minimizing batch time. Alternatively, target values ​​can be set based on the rate of change of any of these characteristics. For example, as shown in Figure 2, as the reaction progresses, the IR peak area of ​​decoupling SiH increases to a maximum value and then levels off. For example, a target value can be set so that the reaction stops when the rate of change of the IR peak area of ​​the decoupling SiH reaches 0% to 10% of its maximum 15-minute average absolute value, which can be measured during the equilibrium reaction. Alternatively, a target value can be set so that the reaction stops when the rate of change of any of the following reaches a predetermined value: the characteristics, the IR peak area of ​​the decoupling SiH, the IR peak height of the decoupling SiH, the IR peak area of ​​the coupling SiH, or the IR peak height of the coupling SiH. The trends of each of these characteristics (or combinations thereof) during the reaction in Example 1 are shown in Figures 2 to 5 below.

[0036] Figure 6 shows the Raman spectrum collected during the reaction of Example 1 described above. The peak area and peak height of the decoupling SiH Raman absorption band increase with increasing reaction time, while the peak height and peak area of ​​the coupling SiH Raman absorption band decrease with increasing reaction time. These peak areas and peak heights can be used to set target values ​​for the SiH reaction termination time, optimize the physical properties of the SiH siloxane, and optimize the reaction batch time. Target values ​​can be set based on the decoupling SiH Raman peak area, decoupling SiH Raman peak height, coupling SiH Raman peak area, and coupling SiH Raman peak height. The reaction can be controlled by stopping the reaction when one or more of these characteristics reach a predetermined target value. Those skilled in the art can set target values ​​for each of these parameters to optimize application performance while minimizing batch time. Alternatively, target values ​​can be set based on the rate of change of any of these characteristics. For example, as shown in Figure 11, as the reaction progresses, the decoupling SiH Raman peak area increases to its maximum value and then begins to level off. A target value can be set to stop the reaction when the rate of change of the decoupling SiH Raman peak area becomes 0 (or close to 0), for example, 0% to 10% of its maximum 15-minute average absolute value measurable during the equilibrium reaction. A target value can also be set to stop the reaction when the rate of change of any of the following reaches a predetermined value: the decoupling SiH Raman peak area, the decoupling SiH Raman peak height, the coupling SiH Raman peak area, or the coupling SiH Raman peak height. The trends of each of these features during the reaction in Example 1 are shown in Figures 7 to 10 below.

[0037] In this Example 2, hexamethyldisiloxane (93.5 g), MeHsiloxane (123.2 g), D4 cyclic compound (207.7 g), and catalyst (4.3 g) were packed into a 500 mL jacketed reactor equipped with an inclined blade impeller and baffles. The reactor head was sealed and an inert atmosphere was established with an N2 blanket. Water flow to the water condenser was turned on, the stirrer was set to 750 RPM, and the reactor jacket temperature was controlled to 60°C using a circulator and heat transfer fluid. IR spectra were collected in situ during the reaction using a Mettler Toledo React IR 15 instrument. After the reaction was carried out for 24 hours, heating was stopped and the reactor contents were cooled to ambient temperature. Upon completion of the reaction, the resulting poly(dimethyl / methylhydrogen)siloxane copolymer had a D:D' (calculated) = 1.5:1 and a DP (calculated) = 12.

[0038] The trend of the IR peak area of ​​the decoupling SiH over time is shown as an example in Figure 15 below. The reaction can be stopped when the IR peak area of ​​the decoupling SiH reaches a predetermined target value. A person skilled in the art can set the target value to optimize the physical properties for a given application while minimizing the batch time. Alternatively, the reaction can be stopped when a target rate of change of the IR peak area of ​​the decoupling SiH over time is reached. The target value of the rate of change can be determined by a person skilled in the art to optimize the physical properties for a given application, as described above in Example 1.

[0039] In this Example 3, hexamethyldisiloxane (44.6 g), MeHsiloxane (857.5 g), and D4 cyclic compound (1032.6 g) were packed into a 2 L jacketed reactor equipped with an inclined blade impeller and baffles. The reactor head was sealed, and an inert atmosphere was established with an N2 blanket. Water flow to the water condenser was turned on, the stirrer was set to 750 RPM, and the reactor jacket temperature was controlled to 60°C using a circulator and heat transfer fluid. Once the temperature setpoint of 60°C was reached, the catalyst (21.3 g) was added to the reactor. IR spectra were collected in situ during the reaction using a Mettler Toledo React IR 15 instrument. After the reaction was carried out for 24 hours, heating was stopped, and the reactor contents were cooled to ambient temperature. Upon completion of the reaction, the resulting poly(dimethyl / methylhydrogen)siloxane copolymer had a D:D' (calculated value) of 1:1 and a DP (calculated value) of 60.

[0040] The trend of the IR peak area of ​​the decoupling SiH over time is shown as an example in Figure 16 below. The reaction can be stopped when the IR peak area of ​​the decoupling SiH reaches a predetermined target value. A person skilled in the art can set the target value to optimize the physical properties for a given application while minimizing the batch time. The reaction can also be stopped when the rate of change of the IR peak area of ​​the decoupling SiH over time reaches a target value. The target value of the rate of change can be determined by a person skilled in the art to optimize the physical properties for a given application, as described above in Example 1.

[0041] In this Example 4, hexamethyldisiloxane (21.43 g), MeHsiloxane (448.0 g), and D4 cyclic compound (1483.6 g) were packed into a 2 L jacketed reactor equipped with an inclined blade impeller and baffles. The reactor head was sealed and an inert atmosphere was established with an N2 blanket. Water flow to the water condenser was turned on, the stirrer was set to 750 RPM, and the reactor jacket temperature was controlled to 60°C using a circulator and heat transfer fluid. Once the temperature setpoint of 60°C was reached, the catalyst (21.3 g) was added to the reactor. IR spectra were collected in situ during the reaction using a Mettler Toledo React IR 15 instrument. After the reaction was carried out for 24 hours, heating was stopped and the reactor contents were cooled to ambient temperature. Upon completion of the reaction, the resulting poly(dimethyl / methylhydrogen)siloxane copolymer had a D:D' (calculated value) of 2.8:1 and a DP (calculated value) of 107.

[0042] The trend of the IR peak area of ​​the decoupled SiH over time for this Example 4 is shown as an example in Figure 13 below. The reaction can be stopped when the IR peak area of ​​the SiH reaches a predetermined target value. A person skilled in the art can set the target value to optimize the physical properties for a given application while minimizing the batch time. The reaction can also be stopped when the rate of change of the IR peak area of ​​the decoupled SiH over time reaches a target value. The target value of the rate of change can be determined by a person skilled in the art to optimize the physical properties for a given application, as described above in Example 1.

[0043] In this Example 5, hexamethyldisiloxane (318.7 g), MeHsiloxane (735.2 g), and D4 cyclic compound (869.4 g) were loaded into a 2 L jacketed reactor equipped with an inclined blade impeller and baffles. The reactor head was sealed, and an inert atmosphere was established with an N2 blanket. Water flow to the water condenser was turned on, the stirrer was set to 750 RPM, and the reactor jacket temperature was controlled to 60°C using a circulator and heat transfer fluid. Once the temperature setpoint of 60°C was reached, the catalyst (21.0 g) was added to the reactor. IR spectra were collected in situ during the reaction using a Mettler Toledo React IR 15 instrument. After the reaction was carried out for 24 hours, heating was stopped, and the reactor contents were cooled to ambient temperature. Upon completion of the reaction, the resulting poly(dimethyl / methylhydrogen)siloxane copolymer had a D:D' (calculated value) of 1:1 and a DP (calculated value) of 12.

[0044] The trend of the IR peak area of ​​decoupling SiH over time is shown as an example in Figure 14. The reaction can be stopped when the IR peak area of ​​SiH reaches a predetermined target value. A person skilled in the art can set the target value to optimize the physical properties for a given application while minimizing the batch time. The reaction can also be stopped when the rate of change of the IR peak area of ​​decoupling SiH over time reaches a target value. The target value of the rate of change can be determined by a person skilled in the art to optimize the physical properties for a given application, as described above in Example 1.

[0045] Examples 1-5 demonstrate that the precise time at which the decoupling SiH peak reaches its maximum value with the minimum rate of change varies depending on several factors, including the molecular weight and D:D' ratio of the starting materials.

[0046] In this Example 6, hexamethyldisiloxane, MeHsiloxane, and D4 cyclic compound were packed into a 500 mL reactor equipped with an inclined blade impeller and baffles, and inactivated with nitrogen. The amounts of each starting material packed into each batch in this example are shown in Table 2 below. The reaction was carried out as follows: The reactor head was tightened and an N2 blanket was supported. The water flow to the water condenser was turned on, the stirrer was set to 750 RPM, and the circulator (reaction temperature: 60°C) was started to control the heating jacket throughout the reaction process. IR spectra were collected in situ using a Mettler Toledo React IR 15 instrument. Each batch was reacted for different times to obtain decoupling SiH at different concentrations as shown in Table 3. To stop the reaction at a specific length of time, the samples were collected and transferred through a filter to remove the catalyst.

[0047] [Table 2]

[0048] Elastomers were synthesized using poly(dimethyl / methylhydrogen)siloxane copolymers prepared in each batch as crosslinking agents. The same hydrosilylation-curable elastomer formulations were prepared for each elastomer formulation, except that copolymers from different batches were used. The curing time (TC90) was measured for elastomers prepared using different copolymers. The curing times for elastomer formulations obtained from different copolymers are shown in Table 3 below.

[0049] [Table 3]

[0050] The data in Table 3 shows that for batches of Example 6, the decoupling SiH peak area increased as the siloxane equilibration reaction time increased (indicating an expansion of the randomization of D and D' units in the copolymer backbone). Expanding the randomization of D and D' units also resulted in a faster curing rate of the elastomer compound in Example 6 (as indicated by the decrease in TC90).

[0051] While not bound by theory, the advantage of the present invention is considered to be that, using this method, it is possible to select a desired degree of randomization of D and D' units in the main chain of the poly(diorgano / organohydrogen)siloxane copolymer produced by this method, while minimizing batch time. When a fast curing rate is desired for elastomer formulations in which the copolymer is used as a crosslinking agent, a high peak area target value, for example, less than 10% of the maximum 15-minute mean absolute change rate, can be selected to obtain a highly random copolymer, thereby accelerating the curing rate of a particular curable elastomer formulation. Alternatively, for example, if copolymers with a more blocky structure are acceptable, the target value can be set to a lower decoupling SiH peak area (or other suitable target value) to minimize the batch time for producing the copolymer.

[0052] Industrial applicability Poly(diorgano / organohydrogen)siloxane copolymers, such as polyorganohydrogensiloxanes produced by the reaction described in U.S. Patent No. 8,686,175, are useful intermediates for the synthesis of various organically functionalized siloxane products. In particular, the product of formula (R2SiO 2 / 2 ) D units and formula (RHSiO 2 / 2 Such copolymers having DH units are useful as crosslinking agents in various curing systems, such as condensation and / or hydrosilylation reaction curable products. The resulting polyorganohydrogensiloxane, as described in U.S. Patent No. 8,686,175, has a blocky main chain structure (e.g., DDDDD H D H DH D H DDD)[In the formula, multiple D units are grouped together, multiple D H The units may be grouped together in "blocks". However, although not bound by theory, the inventors have found that a more random backbone structure (e.g., DDDDD) is possible. H DDDD H DD H DDD H DDDDDDDD H )[wherein the formula, the D units and DH units are more randomly distributed along the main chain], but we have found that this may be desirable for certain applications, such as curable silicone compositions, including hydrosilylated reaction curable silicone elastomer compositions, in which poly(diorgano / organohydrogen)siloxane copolymers may be used. Furthermore, the resulting polyorganohydrogensiloxane, as described in U.S. Patent No. 8,686,175, has D units and D units in the main chain. H The distribution of units may reach the target molecular weight at a different point in time (sometimes considerably earlier) than the random distribution. This can result in a batch-to-batch variation in the "randomness" of the siloxane's main chain structure, which can affect its physical properties and performance. Furthermore, the degree of randomness can affect the performance of the copolymer as a crosslinking agent. As shown in Example 6 above, copolymers with a more random structure produced by the method herein have the advantage of a faster curing rate when incorporated into hydrosilylated reaction-curable elastomer compositions. The method herein can be used both to minimize batch time and to maximize the randomization of poly(diorgano / organohydrogen)siloxane copolymers by appropriately selecting the target value for stopping the reaction in the method herein.

[0053] Definitions and Use of Terms All quantities, ratios, and percentages are based on weight unless otherwise specified. The total amount of all starting materials in a 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 otherwise specified by the context of the specification. The singular form includes the plural form unless otherwise specified. The terms “comprising” and its derivatives, e.g., “comprise” and “comprises,” are used herein in their broadest sense to mean and encompass the view of “including,” “include,” “consisting essentially of,” and “consisting of.” The use of “for example,” “eg,” “such as,” and “including,” which list examples, is not limited to the examples listed. Therefore, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples.

[0054] "Decoupling SiH" and "Decoupling (RHSiO 2 / 2 The term ) is used for other (RHSiO 2 / 2 Formula (RHSiO) in the siloxane backbone of copolymers that are not adjacent to the unit. 2 / 2 It refers to the unit of -(R2SiO). For example, -(R2SiO). 2 / 2 )-(RHSiO 2 / 2 )-(R2SiO 2 / 2 In the )- section, (RHSiO 2 / 2 ) Unit is decoupling (RHSiO 2 / 2Except for completely alternating copolymer backchains, which are undesirable in the equilibration reactions described herein, the more decoupling SiHs there are in the copolymer backchain, the higher the degree of randomness of the copolymer.

[0055] "Coupling SiH" and "Coupling (RHSiO) 2 / 2 The term "RHSiO" is used in other contexts. 2 / 2 ) The formula adjacent to the unit (RHSiO 2 / 2 It refers to the unit of -(RHSiO). For example, -(RHSiO). 2 / 2 )-(RHSiO 2 / 2 )-(RHSiO 2 / 2 In the )- section, (RHSiO 2 / 2 The units are coupled. The more coupling SiH there is in the copolymer, the more blocky the properties become.

[0056] It should be understood that the attached claims are intended to express “modes for carrying out the invention” and are not limited to the specific compounds, compositions, or methods described herein, and may vary between specific embodiments within the scope of the attached claims. With respect to any Markush group on which this specification is used to describe specific features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each member of each Markush group, which is independent of all other Markush members. Each element of a Markush group may be relied upon individually or in combination to provide a suitable basis for a particular embodiment within the scope of the attached claims.

[0057] Any ranges and subranges on which various embodiments of the present invention are relied upon, independently and comprehensively, fall within the scope of the appended claims, and even if integer and / or fractional values ​​are not explicitly stated herein, it is understood that the entire range encompassing such values ​​is described and conceived. Those skilled in the art will readily recognize that the listed ranges and subranges adequately describe and enable various embodiments of the present invention, and that such ranges and subranges can be further divided into related bisections, trisections, quadrisections, quintes, and so on. As merely one example, the range "20-110" can be further detailed into the lower third, i.e., 20-49, the middle third, i.e., 50-79, and the upper third, i.e., 80-110, which individually and collectively fall within the scope of the appended claims, and which may individually and / or collectively rely on and provide appropriate support for specific embodiments within the appended claims. Furthermore, with respect to words that define or modify a range, such as "at least," "greater than," "less than," and "less than or equal to," such words should be understood to include a partial range and / or an upper or lower limit. Moreover, the individual numbers within the disclosed range may be on which and adequately support the specific embodiments within the appended claims.

[0058] The abbreviations used in this specification are defined in Table 5 below.

[0059] [Table 4]

Claims

1. A method for preparing poly(diorgano / organohydrogen)siloxane copolymers, １） A) Formula (R ２ SiO ２／２ ) Source of siloxane units, B) Formula (RHSiO ２／２ ) Source of siloxane units, [In the formula, each R is independently selected from the group consisting of monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups], and C) acid catalyst; By combining starting materials containing, a mixture is formed, 2) By stirring the mixture at a temperature of 20°C to 110°C, a reaction mixture containing the poly(diorgano / organohydrogen)siloxane copolymer is formed via an equilibration reaction, 3) Using vibrational spectroscopy techniques selected from the group consisting of infrared spectroscopy and Raman spectroscopy, decoupling (RHSiO) in the reaction mixture ２／２ ) concentration and coupling (RHSiO) units ２／２ Monitoring the spectral region that includes the absorbance band corresponding to one or both of the concentrations in units, 4) A method comprising stopping the equilibration reaction when a target value related to the absorbance band is reached.

2. The aforementioned target value is, i) Absorption band height, ii) Absorption band area, iii) The rate of change in the height of the absorbance band, iv) The rate of change of the absorbance band area, v) A mathematical conversion value to one or more of i) to iv), and vi) The method according to claim 1, selected from the group consisting of metric chemical analysis values ​​of the spectral region including the absorption band.

3. The method according to claim 2, wherein the target value is the rate of change of the absorbance band height or the rate of change of the absorbance band area, and the rate of change is 0% to 10% of the maximum absolute value that can be measured during the equilibrium reaction.

4. The decoupling (RHSiO ２／２ The method according to claim 2, wherein the absorbance band area is used.

5. Starting materials A) and B) have the unit formula: (R ３ SiO １／２ ), ｔ (R ２ HSiO １／２ ), ｕ (R ２ SiO ２／２ ), ｖ (RHSiO ２／２ ), ｗ (RSiO ３／２ ), ｘ (HSiO ３／２ ), ｙ (SiO ４／２ ), ｚ [where the subscript letters t, u, v, w, x, y, and z represent the amounts of each unit, t ≥ 0, u ≥ 0, v ≥ 1, w ≥ 1, x ≥  0, y ≥ 0, z ≥ 0, provided that the amount (v + w) is from 3 to 300, the amount (x + y + z) is from 0 to a value sufficient to provide up to 20 mol% of the units in the molecule, and the amount (t + u + v + w) ≥ 3]. The method according to claim 1.

6. Starting material A) A1) Unit formula (R ２ SiO ２／２ ) ｃ [In the formula, 3 ≤ c ≤ 12] Cyclic polydiorganosiloxane, A2) Unit formula (R ３ SiO １／２ ) ａ (R ２ HSiO １／２ ) ｄ (R ２ SiO ２／２ ) ｂ A linear polyorganosiloxane containing [wherein each R is independently a monovalent hydrocarbyl group, with amount (a + d) = 2 and 3 ≤ b ≤ 200], and A3) The method according to claim 1, selected from the group consisting of combinations of both A1) and A2).

7. Starting material B) is B1) Unit formula (HRSiO ２／２ ) ｃ A cyclic polyorganohydrogensiloxane [wherein 3 ≤ c ≤ 12] B2) Unit formula (R ３ SiO １／２ ) ａ (R ２ HSiO １／２ ) ｄ (RHSiO ２／２ ) ｅ A linear polyorganosiloxane [wherein each R is independently a monovalent hydrocarbyl group, the amount (a + d) = 2, and 3 ≤ e ≤ 200], and The method according to claim 1, wherein B3) is selected from the group consisting of combinations of both B1) and B2).

8. The method according to claim 1, wherein the poly(diorgano / organohydrogen)siloxane copolymer contains both starting materials A) and B) in the same molecule.

9. The method according to claim 1, which is performed in a batch manner.

10. The method according to claim 1, wherein the catalyst is a heterogeneous catalyst.

11. The method according to claim 1, wherein the starting material in step 1) further comprises D) water.

12. The method according to claim 1, wherein the starting material in step 1) further comprises E) a chelating agent.

13. The aforementioned end-sealing agent has the unit formula: (R ３ SiO １／２ ) ｅ (R ２ HSiO １／２ ) ｆ (R ２ SiO ２／２ ) ｇ (RHSiO ２／２ ) ｈ The method according to claim 12, comprising [wherein the formula, the subscript e is 0, 1, or 2, the subscript f is 0, 1, or 2, the quantity (e + f) = 2, the subscript g ≥ 0, the subscript h ≥ 0, and 0 ≤ (g + h) ≤ 30].

14. The method according to any one of claims 1 to 13, wherein the monitoring in step 3) is performed by real-time and in-situ analysis of the reaction mixture.

15. １） A) Formula (R ２ SiO ２／２ ) Source of siloxane units, B) Formula (RHSiO ２／２ ) Source of siloxane units, [In the formula, each R is independently selected from the group consisting of monovalent hydrocarbyl groups and monovalent halogenated hydrocarbyl groups], and C) acid catalyst; By combining starting materials containing, a mixture is formed, 2) By stirring the mixture at a temperature of 20°C to 110°C, a reaction mixture containing poly(diorgano / organohydrogen)siloxane copolymer is formed via an equilibration reaction, 3) Using vibrational spectroscopy techniques selected from the group consisting of infrared spectroscopy and Raman spectroscopy, decoupling (RHSiO) in the reaction mixture ２／２ ) concentration and coupling (RHSiO) units ２／２ Monitoring the spectral region that includes the absorbance band corresponding to one or both of the concentrations in units, 4) Preparing a poly(diorgano / organohydrogen)siloxane copolymer by stopping the equilibration reaction when a target value related to the absorbance band, which is the rate of change in the absorbance band height or the rate of change in the absorbance band area, is reached, having a value of 0% to 10% of the maximum absolute value that can be measured during the equilibration reaction process. A method comprising using the aforementioned poly(diorgano / organohydrogen)siloxane copolymer as a crosslinking agent in a curable silicone formulation.

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