Low-isomer hydrosilylation

Abstract

The reaction composition comprises (a) a compound of the formula: CH2=CHCH2O-A a an allyl polyether having the formula -B, wherein (i) subscript a is 2 to 170; (ii) A is selected from -CH2CHO-, -CH2CH(CH3)O-, -CH(CH3)CHO-, CH2CH(CH2CH3)O-, -CH(CH2CH3)CHO-, -CH2CF(CF3))O-, -CF(CF3)CF2O-, and -CF2CF(CF3)O; and (iii) B is selected from -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(O)CH3, and -CF2CF2CF3; and (b) the following siloxane units: [R2HSiO 1 / 2 ] m [R2SiO 2 / 2 ] d [RSiO 3 / 2 ] t [SiO4 / 2] q wherein d+t+q is 1 or greater; (i) R is selected from hydrocarbyl groups having 1 to 8 carbon atoms; (ii) subscript m is 2 or greater; (iii) subscript d is 0 to 20; (iv) subscript t is 0 to 2; and (v) subscript q is 0 to 2; and (c) a platinum-based hydrosilylation catalyst, wherein there are at least 4 molar equivalents of silyl hydride functionality relative to allyl functionality in the reaction composition.

Description

Technical Field

[0001] The present invention relates to a reaction composition suitable for carrying out hydrosilylation with little or no by - products of alkene reactant isomers in the final product.

[0002] Introduction section The hydrosilylation reaction is a combination reaction that occurs between an alkene, typically a terminal alkene, and a silyl hydride species. The hydrosilylation reaction is generally catalyzed using a platinum - based catalyst. An exemplary hydrosilylation reaction can be shown, for example, as follows:

Chemical formula

[0003] When the alkene is an allyloxy group, a part of the allyl group has a tendency to reversibly isomerize under hydrosilylation reaction conditions, typically generating cis and trans 2 - alkene isomers that are non - reactive towards hydrosilylation.

Chemical formula

[0004] It is common for approximately 15 mole percent (mol%) or more of the allyl groups to carry over with the reaction product as unwanted 2 - alkene isomer by - products. Of particular concern is that the 2 - alkene isomer by - products are associated with an offensive odor in the final product, especially in the hydrosilylation reaction with allyl polyethers, perhaps due to the decomposition of the isomers to propionaldehyde (see, for example, US8877886).

[0005] The hydrosilylation reaction is often carried out with an excess of allyl groups that are at least partly responsible for the formation of non-reactive isomerization by-products. As a result, all of the silyl hydride groups tend to react during the reaction to produce products that do not contain silyl hydride groups. Such reactions are not suitable when attempting to prepare products that retain terminal Si-H bonds for use in further reactions.

[0006] It is desirable to identify a hydrosilylation reaction process using allyl polyethers that results in less than 5 mol%, preferably less than 3 mol%, and even more preferably less than 1 mol% of allyl polyether remaining as a 2-alkene by-product. It is even more desirable to identify such a process that produces a reaction product having an Si-H bond, thereby enabling the reaction product to be used as a reactant in a further hydrosilylation reaction. SUMMARY OF THE INVENTION

[0007] The present invention provides a solution to the problem of carrying out a hydrosilylation reaction using allyl polyethers that results in less than 5 mol% of allyl polyether remaining as a 2-alkene by-product, and can result in 3 mol% or less, and even 1 mol% or less of allyl polyether. Moreover, the hydrosilylation reaction produces a reaction product having an Si-H bond, thereby enabling the reaction product to be used as a reactant in a further hydrosilylation reaction. These are the desired results.

[0008] Even more surprisingly and beneficially, the present invention provides for a reaction time of 48 hours or less, 24 hours or less, and in some cases 12 hours or less, 10 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, and even 2 hours or less, while at the same time a reaction time of 1 hour or more, typically 2 hours or more, while at the same time an execution at a reaction temperature of 250 degrees Celsius (°C) or less, 200 °C or less, 180 °C or less, 150 °C or less, 140 °C or less, 130 °C or less, 120 °C or less, and even 110 °C or less, and at the same time a platinum catalyst concentration of 500 parts per million by weight (ppm) or less, even 100 ppm or less, 75 ppm or less, 50 ppm or less, 25 ppm or less, and even 10 ppm or less, typically based on the weight of the reaction composition, a platinum catalyst concentration of 1 ppm or more, 2 ppm or more, 5 ppm or more, and preferably 7.5 ppm or more, 10 ppm or more, and even 20 ppm or more to achieve the target result.

[0009] The present invention is the result of discovering that a reaction can be carried out to achieve the target characteristics when the molar ratio of the silyl hydride functional group to the allyl functional group is 4 or more for a specific silyl hydride. The silyl hydride is two or more (CH3)2HSiO separated by at least one siloxane group 1 / 2 siloxane group (M' group), preferably at least one (CH3)2SiO 2 / 2 and must contain no siloxane group (D group). This reaction needs to be carried out in an excess of silyl hydride functional groups instead of the general process of carrying out the reaction in an excess of allyl.

[0010] Surprisingly, it has been discovered that purifying the allyl ether prior to carrying out the hydrosilylation reaction enables the target result to be achieved more quickly at a lower temperature and with less platinum-based catalyst than when the allyl ether is not purified.

[0011] In a first aspect, the present invention provides a reaction composition comprising (a) an allyl polyether having the following formula: CH2=CHCH2O-A a -B Wherein, (i) the subscript a is the average number of consecutive A units per molecule, and has a value in the range of 2 to 170, (ii) A is independently, in each occurrence, selected from the group consisting of -CH2CH2O-, -CH2CH(CH3)O-, -CH(CH3)CH2O-, CH2CH(CH2CH3)O-, -CH(CH2CH3)CH2O-, -CH2CF(CF3)O-, -CF(CF3)CF2O-, and -CF2CF(CF3)O-, (iii) B is selected from the group consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(O)CH3, -CF3, and -F, an allyl polyether, and (b) for each siloxane unit per molecule, a silyl hydride-functional siloxane selected from those containing the following siloxane units in the following average number ranges, [R2HSiO 1 / 2 m [R2SiO 2 / 2 d [RSiO 3 / 2 t [SiO4 / 2] q Wherein, the sum of the subscripts d, t, and q is 1 or more, (i) R is independently, in each occurrence, selected from hydrocarbyl groups having 1 to 8 carbon atoms, (ii) the subscript m is the average number of R2HSiO 1 / 2 groups per molecule, and is 2 or more, (iii) the subscript d is the average number of R2SiO 2 / 2 groups per molecule, and is 0 or more and 20 or less, (iv) the subscript t is the average number of RSiO 3 / 2 groups per molecule, and is 0 or more and 2 or less, (v) the subscript q is the average number of SiO 4 / 2 groups per molecule, and is 0 or more and 2 or less, a silyl hydride-functional siloxane, and (c) a platinum-based hydrosilylation catalyst, and contains at least 4 molar equivalents of silyl hydride functional groups relative to the allyl functional groups in the reaction composition, a reaction composition.

[0012] ​​​In a second aspect, the present invention is a process comprising the steps of: (a) providing a reaction composition of the first aspect; and (b) heating the reaction composition to a temperature in the range of 80 to 250 degrees Celsius for at least 1 hour.

[0013] In a third aspect, the present invention is a reaction product of the process of the second aspect, characterized in that it contains 2-alkene polyether at a concentration of less than 5 mole percent of the concentration of allyl polyether before heating at 80 degrees Celsius.

[0014] The method of the present invention generates a reaction product containing less than 5 mol% of allyl ether as a 2-alkene by-product without removing any of the by-products after the reaction. In fact, when the allyl ether used in the hydrosilylation reaction has three or more consecutive ether groups per molecule, the reaction product cannot be purified by removing the 2-alkene isomer of allyl ether. Therefore, the only way to prepare such a reaction product is by the process of the present invention. Thus, when the hydrosilylation reaction product contains a reacted allyl ether component containing three or more consecutive ether groups and then contains less than 5 mol% of allyl ether reactant as the 2-alkene isomer of allyl ether, it is necessarily made by the process of the present invention.

[0015] The process of the present invention is useful for preparing polyether-functional polysiloxanes, particularly polyether-functional polysiloxanes further containing silyl hydride functionality, while at the same time providing less than 5 mol% of vinyl-functional polyether reactants that form 2-alkene polyether impurities that are commonly present with the hydrosilylation product.

Mode for Carrying Out the Invention

[0016] Where a test method is indicated without a test method number and a date, it refers to the latest test method at the priority date of this document. A reference to a test method includes both a reference to the test society and a test method number. In this specification, the following abbreviations and identifiers for test methods apply: ASTM refers to the American Society for Testing and Materials, EN refers to the European Norm, DIN refers to the Deutsches Institut fur Normung, ISO refers to the International Organization for Standards, and UL refers to the Underwriters Laboratory.

[0017] Products identified by their trade names refer to the compositions available under those trade names at the priority date of this document.

[0018] "A number" means two or more. "And / or" means "and, or alternatively". Unless otherwise specified, all ranges include the endpoints. Unless otherwise expressly stated, all weight percent (wt%) values are relative to the weight of the composition, and all volume percent (vol%) values are relative to the volume of the composition.

[0019] As used herein, "hydrocarbyl" includes both substituted and unsubstituted hydrocarbyl groups. A substituted carbyl group has one or more hydrogen atoms or carbon atoms replaced by another atom or group other than hydrogen and carbon. Desirably, unless otherwise specified, hydrocarbyl is an unsubstituted hydrocarbyl.

[0020] allyl polyether The reaction composition of the present invention includes an allyl polyether having the following formula, CH2=CHCH2O-A a -B wherein, (i) The subscript a is the average number of consecutive A units per molecule and is 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 15 or more, 20 or more, 25 or more, 50 or more, 75 or more, 100 or more, and at the same time, generally 170 or less, 150 or less, 125 or less, 100 or less, 75 or less, 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, and further 5 or less, 4 or less, or 3 or less, (ii) A is independently, in each occurrence, selected from the group consisting of -CH2CH2O-, -CH2CH(CH3)O-, -CH(CH3)CH2O-, CH2CH(CH2CH3)O-, -CH(CH2CH3)CH2O-, -CH2CF(CF3)O-, -CF(CF3)CF2O-, and -CF2CF(CF3)O-. To avoid misunderstanding, the allyl polyether can include all one type of A unit, or a combination of two or more types of A units. (iii) B is selected from the group consisting of -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(O)CH3, and -CF2CF2CF3.

[0021] Examples of suitable allyl polyethers include CH2=CHCH2O(CH2CH2O) 11 CH3, CH2=CHCH2O(CH2CH(CH3)O)2CH3, CH2=CHCH2O(CH2CH2O) 11 (CH2CH(CH3)O)4H, CH2=CHCH2O(CH2CH2O) 18 (CH2CH(CH3)O)5CH3, CH2=CHCH2O(CH2CH2O) 24 (CH2CH(CH3)O)5CH3, CH2=CHCH2O(CH2CH2O) 24 (CH2CH(CH3)O) 21 C(O)CH3, CH2=CHCH2O(CH2CH2O) 24 (CH2CH(CH3)O) 24 CH3, and CH2=CHCH2OCH2CF(CF3)O(CF2CF(CF3)O) 10Either or any combination of two or more allyl polyethers selected from the group consisting of CF2CF2CF3 is included.

[0022] When the allyl polyether is purified, the hydrosilylation reaction with the allyl polyether becomes more efficient. For example, the allyl polyether is purified by exposing it to a purification agent, such as passing the allyl polyether through a bed of the purification agent or mixing the purification agent with the allyl polyether to form a slurry and then filtering off the purification agent. The purification of the allyl polyether by exposure to the purification agent can occur before, during, or before and during the heating of the allyl polyether during the hydrosilylation reaction.

[0023] Suitable purification agents include any one or any combination of two or more components selected from the group consisting of alumina, zeolite, activated carbon, and silica alumina. The efficiency is demonstrated by hydrosilylation that is completed in a shorter time and / or at a lower temperature and / or with a lower platinum catalyst input amount than the same hydrosilylation reaction using the allyl polyether without purification. In the hydrosilylation reaction of the present invention, the hydrosilylation reaction efficiency is further characterized by achieving a reaction product having a molar percentage of allyl groups of less than 5 mol%, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, at a faster time and / or a lower temperature than the same reaction with the unpurified allyl polyether and having a 2-alkene isomer. Therefore, it is desirable to purify the allyl polyether before carrying out the hydrosilylation reaction using the allyl polyether.

[0024] Silyl hydride functional siloxane The present invention includes a silyl hydride functional siloxane. A silyl hydride functional siloxane preferably comprising, and more preferably consisting of, the following siloxane units in the following average number ranges per siloxane unit per molecule: [R2HSiO 1 / 2 m [R2SiO 2 / 2 d [RSiO​​3 / 2 t [SiO4 / 2] q wherein the sum of the subscripts d, t, and q is 1 or more, (i) R is independently, in each occurrence, selected from hydrocarbyl groups having 1 or more carbon atoms, 2 or more carbon atoms, 3 or more carbon atoms, 4 or more carbon atoms, 5 or more carbon atoms, 6 or more carbon atoms, and even 7 or more carbon atoms, while simultaneously having 8 or fewer carbon atoms. Desirably, R is independently, in each occurrence, selected from a methyl group and a phenyl group. More preferably, R is, in each occurrence, a methyl group. (ii) The subscript m is the average number of R2HSiO 1 / 2 units per molecule, is 2 or more, and at the same time, generally is 20 or less, 15 or less, 10 or less, 8 or less, 6 or less, 5 or less, 4 or less, and even 3 or less. (iii) The subscript d is the average number of R2SiO 2 / 2 units per molecule, is 0 or more, preferably 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, and even 10 or more, while simultaneously, typically is 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, and even 3 or less. (iv) The subscript t is the average number of RSiO 3 / 2 units per molecule, is 0 or more, can be 1 or more, while simultaneously, generally is 2 or less, and even 1 or less. (v) The subscript q is the average number of SiO 4 / 2 units per molecule, is 0 or more, can be 1 or more, while simultaneously, generally is 2 or less, and even 1 or less.

[0025] Desirably, the silyl hydride functional siloxane has the following formula, [R2HSiO 1 / 2 m [R2SiO 2 / 2 d wherein m = 2, and d is the R2SiO per molecule 2 / 2 ​​​is the average of the groups, is 1 or more, 2 or more, and 20 or less, preferably 18 or less, can be 16 or less, and R is independently, in each occurrence, selected from hydrocarbyl groups having 1 to 8 carbon atoms, and preferably, R is methyl in each occurrence. The silyl hydride functional siloxane has the formula [(CH3)2HSiO 1 / 2 2[(CH3)2SiO 2 / 2 1, and [(CH3)2HSiO 1 / 2 2[(CH3)2SiO 2 / 2 16 and can be selected from those having

[0026] What is unique and important to the performance of the reaction composition of the present invention is that the silyl hydride functional siloxane is present in a concentration sufficient to provide at least 4 molar equivalents of silyl hydride functional groups relative to the allyl functional groups in the reaction composition. Having an excess of silyl hydride functional groups promotes at least two results: (1) the reaction product, on average, has at least one silyl hydride functional group per molecule, which enables it to be used as the silyl hydride component in subsequent hydrosilylation reactions, and (2) there is sufficient silyl hydride to react with all of the allyl groups. The second result is important because isomerization between allyl and the 2-alkene isomer of allyl is thought to be reversible, meaning that if allyl isomerizes to the 2-alkene isomer during the hydrosilylation reaction, there should be silyl hydride present to react with the 2-alkene isomer when it isomerizes back to allyl. Thus, an excess of silyl hydride enables essentially all of the allyl functional groups to be consumed rather than leaving some as 2-alkene isomer by-products.

[0027] Platinum-based hydrosilylation catalyst ​The present invention includes a platinum-based hydrosilylation catalyst. Such catalysts are well known in the art, and in the broadest scope of the present invention, there are no restrictions on which platinum-based hydrosilylation catalyst or combination of such catalysts will function as the platinum-based hydrosilylation catalyst of the present invention. Examples of suitable platinum-based hydrosilylation catalysts include Speier's catalyst (H2PtCl6), Karstedt's catalyst (an organoplatinum compound derived from a divinyl-containing disiloxane), and any one or any combination of two or more selected from the group consisting of platinum-based catalysts encapsulated with a phenyl resin of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex.

[0028] Generally, when the concentration of the platinum-based catalyst is high, the hydrosilylation reaction becomes faster, and the desired reaction product and the target level of 2-alkene isomers are achieved faster and / or at a lower temperature than when using a lower concentration of the catalyst. The target result can be achieved using a platinum-based catalyst concentration of 1 part per million by weight (ppm) or more, preferably 2 ppm or more, 4 ppm or more, 6 ppm or more, 7 ppm or more, 7.5 ppm or more, 10 ppm or more, 15 ppm or more, 20 ppm or more, 30 ppm or more, 40 ppm or more, 50 ppm or more, 60 ppm or more, 70 ppm or more, 80 ppm or more, 90 ppm or more, 100 ppm or more, 150 ppm or more, 200 ppm or more, 300 ppm or more, and even 400 ppm or more. Technically, there is no known upper limit regarding the concentration of the platinum-based catalyst that can be used. However, in terms of cost, it is generally recommended to use as little platinum-based catalyst as possible. Therefore, while selecting one lower limit from the above list for the platinum catalyst, the concentration of the platinum-based catalyst is generally 500 ppm or less, 400 ppm or less, 300 ppm or less, 200 ppm or less, and even 100 ppm or less, 75 ppm or less, 50 ppm or less, 25 ppm or less, and even 10 ppm or less. The concentration of the platinum-based catalyst is proportional to the weight of the reaction composition.

[0029] Hydrosilylation reaction process The reaction composition of the present invention is useful for carrying out a hydrosilylation reaction process having the above-described target results, and this process is another aspect of the present invention.

[0030] The process of the present invention includes: (a) providing the reaction composition of the present invention; and (b) heating the reaction composition to a temperature of 80 to 250 degrees Celsius (°C) for 1 hour or more.

[0031] The reaction process can be carried out in a solvent, which will preferably involve adding the solvent to the reaction mixture before the heating step. Suitable solvents for the hydrosilylation reaction include any one or any combination or two or more selected from the group consisting of toluene, 2-propanol, 1,3-bis(trifluoromethyl)benzene, and α,α,α-trifluoromethylbenzene.

[0032] The step of providing the reaction composition preferably includes purifying the allyl polyether before the heating step, preferably before combining the allyl polyether with the silyl hydride-functional siloxane and / or the platinum-based catalyst. The method for purifying the allyl polyether is described above. Purifying the allyl polyether before carrying out the hydrosilylation reaction tends to achieve the desired reaction product and the target level of 2-alkene isomers faster and / or at a lower temperature than when using a less purified allyl polyether.

[0033] The reaction composition can be provided by combining an allyl polyether with a silyl hydride and a platinum-based catalyst. Desirably, the reaction composition is mixed to obtain a reaction composition that is as homogeneous as possible. Generally, the components of the reaction composition can be added in any order. For example, an allyl polyether can be combined with a silyl hydride-functional siloxane to form a reaction mixture, and then a platinum-based catalyst can be added to the reaction mixture. Alternatively, the platinum-based catalyst can be added to either or both of the allyl polyether and the silyl hydride-functional siloxane, and then the allyl polyether can be combined with the silyl hydride-functional siloxane. Alternatively, all three components can be added to each other simultaneously.

[0034] The reaction composition is prepared at a temperature below 80°C, preferably 70°C or lower, 60°C or lower, 50°C or lower, 40°C or lower, 30°C or lower, 25°C or lower, 23°C or lower, and even 20°C. The hydrosilylation reaction is less likely to proceed at a colder temperature, and generally, it is desirable to prepare the reaction composition without any significant hydrosilylation reaction activity until the desired reaction is achieved by heating the reaction composition.

[0035] To efficiently induce the hydrosilylation reaction with the reaction composition of the present invention and achieve a product having less than 5 mol% of allyl polyether remaining as a 2-alkene isomer, the reaction composition is heated to 80°C or higher, preferably 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, and even 130°C or higher, while at the same time heating to 250°C or lower, 200°C or lower, and even 150°C or lower, 130°C or lower, 110°C or lower. The hydrosilylation reaction typically proceeds faster and produces a product with the target properties from the reaction composition more rapidly at a higher temperature. At a lower reaction temperature, especially when a fast reaction is desired, it is desirable to consider purifying the allyl polyether and / or using a higher concentration of the platinum-based catalyst to produce a product with the target properties more rapidly.

[0036] Surprisingly, the process of the present invention achieves the target result, and even more surprisingly, at the temperatures and platinum-based catalyst concentrations taught herein, the target result can be achieved by heating for 48 hours or less, 24 hours or less, 12 hours or less, 10 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, and even 2 hours or less, while at the same time generally for 1 hour or more, typically 2 hours or more.

[0037] Since this process is carried out with an excess of silyl hydride, the hydrosilylation reaction can produce a product mix that contains unreacted silyl hydride functional siloxanes remaining after the hydrosilylation reaction is complete and mixed with the hydrosilylation reaction product. The process of the present invention may further include a step of removing unreacted silyl hydride functional siloxanes from the hydrosilylation reaction product. A method for removing unreacted silyl hydride functional siloxanes includes applying a vacuum to the hydrosilylation reaction product mix. The unreacted silyl hydride functional siloxanes have a higher vapor pressure than the hydrosilylation reaction product and can be evaporated from the reaction product under vacuum. Applying heat under vacuum can further facilitate the evaporation of the unreacted silyl hydride functional siloxanes.

[0038] Reaction product The reaction product of the process of the present invention is a polyether-functionalized siloxane that also contains one or two or more silyl hydride functional groups. Moreover, this process results in 2-alkene isomers of allyl polyether that are less than 5 mol%, preferably 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, relative to the amount of starting allyl polyether, and it may not contain it. 1 H, 13 C, and 29Using Si nuclear magnetic resonance (NMR) spectroscopy, the amount of 2-alkene isomers of allyl polyether relative to the amount of starting allyl polyether is determined to determine both the relative molar amount of polyether bonded to the polysiloxane relative to the polysiloxane molecule (“[bonded alkene]”), and the relative amount of 2-alkene isomers relative to the polysiloxane molecule (“[isomer alkene]”). The mole % 2-alkene isomer is {[isomer alkene] / ([isomer alkene] + [bonded alkene])} x 100%.

[0039] The benefit of the process of the present invention is that this process produces a hydrosilylation reaction product having far fewer 2-alkene isomer by-products than similar hydrosilylation reactions. Moreover, the reaction product contains a silyl hydride functional group. As a result, the reaction product can be used directly as a silyl hydride functional reactant in further hydrosilylation reactions, without carrying a large amount of 2-alkene isomer by-products with the reaction product.

[0040] In that regard, the hydrosilylation reaction between allyl polyether and silyl hydride functional polysiloxane can be a first hydrosilylation reaction that generates a first hydrosilylation product having silyl hydride functionality. The alkene functional (preferably vinyl or allyl) siloxane can be added after heating step (b), preferably after heating step (b) has been for a time sufficient for all of the allyl groups of the allyl polyether to react when forming the first hydrosilylation product, and then heated to carry out a second hydrosilylation reaction between the first hydrosilylation product and the alkene functional siloxane to produce a second hydrosilylation product.

[0041] The alkene functional siloxane for use in the second hydrosilylation reaction can be, for example, an alkene functional linear siloxane (such as vinyl functionalized polydimethylsiloxane) or an alkenyl functional resin. Desirably, the alkene functional siloxane has the following formula, [R3SiO 1 / 2m [R2SiO 2 / 2 d [RSiO 3 / 2 t [[SiO4 / 2] q In the formula, at least one R contains an alkenyl group, m = 0 to 50 (preferably 1 to 50), d = 1 to 2000, t = 0 to 30, and q = 0 to 60.

[0042] This second reaction is particularly beneficial for efficiently producing polyether-functional resins such as polyether-functional MQ resins and for producing such resins having low 2-alkene isomer by-products. It is rare to have a polyether having a silyl hydride functional group and particularly a very low 2-alkene isomer content. Thus, the first hydrosilylation product is useful for reacting with an MQ resin having an alkenyl (e.g., vinyl or allyl) functional group by hydrosilylation to produce a polyether-functional MQ resin having low 2-alkene isomer by-products. Such resins are desirable in many applications where low by-product levels are required, including health and beauty products, including creams, cosmetics, lotions, and cleansing products.

[0043] The second hydrosilylation product can be useful, for example, as an emulsifier, dispersant, and compatibilizer in beauty care, oil and gas extraction, and polyurethane foam additives. They are also utilized in paints, inks, and coatings as defoamers, leveling agents, and slip and scratch additives. Other uses include agricultural adjuvants, screw lubricants, detergents, metalworking, and automotive care. The benefit of preparing the second hydrosilylation product according to the method of the present invention is that the second hydrosilylation product contains very little (less than 5 mol% of the original allyl polyether) as a 2-alkene isomer or subsequent reaction product of a 2-alkene isomer. This is desirable for reducing odors in the final product and applications.

Examples

[0044] Table 1 lists the components used in the following examples and comparative examples.

Table 1

[0045] Sample preparation The following table provides specific information about the reactions of each sample. Generally, a total reaction composition amount in the range of 3 grams to 500 grams is used to prepare the sample in a glass reaction vessel. In the glass reaction vessel, the silylhydride-functional siloxane and allyl polyether are slowly combined at a concentration suitable to achieve the specified molar equivalent of the silylhydride functional group relative to the allyl functional group. A polytetrafluoroethylene stirring bar is inserted. The glass reaction vessel is sealed with a septum and heated to the indicated reaction temperature. A solution of the catalyst (0.1 wt% Karstedt's catalyst in toluene) is injected and maintained at the indicated reaction temperature for the indicated time. The resulting product is characterized for its 2-alkene isomer content, and the solvent and excess silylhydride-functional siloxane are removed under vacuum.

[0046] Characterization of isomer content Using a 400 megahertz magnet 1 1H NMR spectroscopy is used to evaluate the sample for its isomer content. For analysis, the sample is diluted in d6-benzene. The peaks of the isomers are at δ 5.85 ppm and δ 6.17 ppm in the NMR spectrum.

[0047] Demonstration of the invention using various allyl polyethers Samples 1-11 demonstrate the versatility of the present invention using different allyl polyethers. Each sample was prepared using the same silyl hydride reactant (SiH SF1) and 9 molar equivalents of SiH relative to the allyl functionality for consistency. The samples demonstrate the ability to prepare reaction products having less than 5 mol%, actually 3 mol% or less, remaining as the 2-alkene isomer and mostly 0 mol% allyl polyether according to the present invention. Table 2 presents the formulation information, reaction conditions (concentration of platinum catalyst, reaction temperature, and reaction time), and the resulting mol% of allyl polyether remaining as the 2-alkene isomer for Samples 1-11. [Table 2]

[0048] Table 3 provides the reaction information for Samples 13 and 14. Table 3 reveals the benefit of purifying the allyl polyether prior to performing the hydrosilylation reaction. Sample 12 in Table 2 demonstrates that Allyl PE8 can result in a reaction product without 2-alkene isomers. Sample 13 shows that when the same reaction is carried out with less catalyst, it can result in 2-alkene isomers when run for 7 hours. Sample 14 shows that by first purifying the allyl polyether, the reaction of Sample 13 does not result in 2-alkene isomers in the final product. The allyl polyether was purified by passing it through an alumina column. [Table 3]

[0049] Demonstration of the Importance of the Silyl Hydride Type Table 4 provides the reaction information for Samples 15-18. Each of these reactions uses Allyl PE1 as the allyl polyether. [Table 4]

[0050] Samples 15 and 16 show that when the silyl hydride functional group is on the D-type siloxane unit ((CH3)HSiO 2 / 2 ) but not on the M-type siloxane unit (R3SiO 1 / 2 ), then the hydrosilylation reaction, even when carried out in an excess of silyl hydride functional groups, results in more than 5 mol% of allyl polyether that forms the 2-alkene isomer.

[0051] Samples 17 and 8 show that when the silyl hydride functional siloxane contains only the M' unit ((CH3)2HSiO 1 / 2 ), then the hydrosilylation reaction, even when carried out in an excess of silyl hydride functional groups, results in more than 5 mol% of allyl polyether that forms the 2-alkene isomer.

[0052] Demonstration of the invention using various silyl hydride types Table 5 provides reaction information for Samples 3, 19, and 20, demonstrating various silyl hydride functional siloxanes having a silyl hydride functional group on the M-type siloxane unit. Each of Samples 3, 19, and 20 uses Allyl PE1 as the allyl polyether. Each of the silyl hydride functional siloxanes having a silyl hydride on the M-type siloxane unit provides the target properties of the present invention.

Table 5

[0053] Demonstration of the importance of the SiH:allyl ratio Table 6 provides reaction information for Samples 21 - 23. Each of the samples uses SiH FS1 and Allyl PE1 as reactants. The results show the importance of using more than 2 equivalents of SiH functional groups relative to the allyl functional group. At 2 molar equivalents, Sample 21 cannot achieve the target 2-alkene isomer level even after reacting for 24 hours. Note that Sample 22 avoids any 2-alkene isomers using a reaction time of 14 hours at 4 equivalents, and Sample 23 avoids 2-alkene isomers using a reaction time of 8 hours at 8 equivalents.

Table 6

[0054] Reaction time Table 7 provides the reaction characteristics for pairs of reactions showing how reaction time affects the formation of 2-alkene isomers. Generally, higher temperature and longer reaction time result in fewer 2-alkene isomers, with all else held constant.

Table 7

[0055] These results indicate that a reaction time of at least 2 hours is desirable to result in an allyl polyether of 5 mol% or less that forms 2-alkene isomers in the final reaction product.

[0056] Subsequent hydrosilylation reaction One of the benefits of the present invention is to not only convert less than 5 mol% of the starting allyl polyether to 2-alkene isomers in the reaction product, but also to provide a means to form a hydrosilylation reaction product containing a silyl hydride on the M-type siloxane units where the reaction product can be used in subsequent hydrosilylation reactions.

[0057] Samples 33 - 36 illustrate a process where the reaction product of the initial hydrosilylation reaction according to the present invention is subsequently used in another hydrosilylation reaction with a vinyl-functional polysiloxane.

[0058] Sample 33. To a 500 milliliter (mL) flask, 50.0 grams (g) of the reaction product of Sample 10 without further purification was added, (CH3)3SiO((CH3)2SiO) 1.2 ((CH3)(CH2=CH-)SiO) 1.2 OSi(CH3)3 (also known as "MD 1.2 D vi 1.2Add it together with 67.1 g of "M". Add a polytetrafluoroethylene stirring bar. Seal the flask with a rubber septum, purge with an inert gas, and heat at 110 °C for 5 hours. 1 1H NMR spectroscopy reveals that 99% of the SiH groups are consumed and the hydrosilylation reaction product is isolated as a colorless and transparent oil.

[0059] Prepare the MD 1.2 D vi 1.2 reactants in a 1-liter round-bottom flask. Combine 260 grams of polydimethylsiloxane with a viscosity of 0.65 centistokes (cSt), 154 grams of D4 polysiloxane (e.g., DOWSIL 1-2287 intermediate manufactured by The Dow Chemical Company), 133 grams of D4 polysiloxane (e.g., DOWSIL 244 fluid manufactured by The Dow Chemical Company), and 0.1 weight percent potassium hydroxide in the flask. Purge with an inert gas and heat to 140 °C for 4 hours. Cool the reaction mixture and neutralize with phosphoric acid. Stir in the whole sodium bicarbonate and filter to obtain the MD vi D 1.2 D vi 1.2 M product.

[0060] Sample 34. Add 92.9 grams (g) of the reaction product of Sample 10 without further purification to a 500 milliliter (mL) flask, along with 45 g of (CH3)3SiO((CH3)2SiO) 3.1 ((CH3)(CH2=CH-)SiO) 3.7 OSi(CH3)3 (alias "MD 3.1 D vi 3.7 M"). Add a polytetrafluoroethylene stirring bar. Seal the flask with a rubber septum, purge with an inert gas, and heat at 110 °C for 5 hours. 1 1H NMR spectroscopy reveals that 99% of the SiH groups are consumed and the hydrosilylation reaction product is isolated as a colorless and transparent oil.

[0061] Prepare the MD in a 1 liter round bottom flask. 3.1 D vi 3.7 Prepare the M reactant. Combine 300 grams of 2 cSt polydimethylsiloxane, 226 grams of D vi 4 polysiloxane (e.g., DOWSIL 1-2287 intermediate from The Dow Chemical Company), and 0.1 weight percent potassium hydroxide in the flask. Purge with an inert gas and heat at 140 °C for 4 hours. Cool the reaction mixture and neutralize with phosphoric acid. Stir in sodium bicarbonate and filter to obtain the MD 3.1 D vi 3.7 M product.

[0062] Sample 35. In a 40 mL drum container, add 92.9 g of the product of Sample 10 without further purification, together with 2.18 g of (CH3)3SiO((CH3)2SiO) 124 ((CH3)(CH2=CH-)SiO) 12 OSi(CH3)3 (alias "MD 124 D vi 12 M"). Add a polytetrafluoroethylene stir bar. Seal the flask with a rubber septum, purge with an inert gas, and heat to 110 °C for 3 hours. 1 1H NMR spectroscopy reveals that 99% of the SiH groups are consumed and the hydrosilylation reaction product is isolated as a colorless transparent oil.

[0063] Prepare the MD in a 1 liter round bottom flask. 124 D vi 12 Prepare the M reactant. 21 grams of 2 cSt polydimethylsiloxane, D vi4 grams of polysiloxane (e.g., DOWSIL 1-2287 intermediate manufactured by The Dow Chemical Company), 486 grams of D4 polysiloxane (e.g., DOWSIL 244 fluid manufactured by The Dow Chemical Company), and 0.1 weight percent of potassium hydroxide in the flask are combined. Purge with an inert gas and heat to 140 °C for 4 hours. Cool the reaction mixture and neutralize with phosphoric acid. Stir the entire sodium bicarbonate and filter to obtain the MD 124 D vi 12 product.

[0064] Sample 36. To a 500 milliliter (mL) flask, add 20 g of 2-propanol, 4.77 g of the reaction product of Sample 11 without further purification, and 100 g of a vinyl-functional MQ resin having a weight average molecular weight of 25,000 daltons (by gel permeation chromatography), 5 to 6 mol% vinyl relative to silicon atoms, and a combined -OH and -OCH(CH3)2 groups of 6 to 8 mol%. Seal with a rubber septum, purge with an inert gas, and heat to 60 °C. Add 0.2 g of Karstedt's catalyst (1 wt% in toluene) to the reaction mixture. Heat to 82 °C for 3 hours. 1 The 1H NMR spectrum reveals complete reaction of the SiH functional groups.

[0065] Paragraphs of WO2010 / 079366

[0066] ~

[0067] and paragraphs of US2676182

[0068] ~

[0069] The vinyl-functional MQ resin is prepared by any method known in the art, including the methods of

Claims

1. A reaction composition comprising: (a) an allyl polyether having the following formula: CH ２ =CHCH ２ O-A ａ -B In the formula: (i) the subscript a is the average number of consecutive A units per molecule and has a value in the range of 2 to 170; (ii) A, independently, in each occurrence, is -CH ２ CH ２ O-, -CH ２ CH(CH ３ )O-, -CH(CH ３ )CH ２ O-, CH ２ CH(CH ２ CH ３ )O-, -CH(CH ２ CH ３ )CH ２ O-, -CH ２ CF(CF ３ )O-, -CF(CF ３ )CF ２ O-, and -CF ２ CF(CF ３ )O-; and is selected from the group consisting of (iii) B is -H, -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH ２ CH ２ CH ２ CH ３ , -C(O)CH ３ , and -CF ２ CF ２ CF ３ selected from the group consisting of, allyl polyether, and (b) having the following formula: [R₂HSiO₁ / ₂]m[R₂SiO₂ / ₂]d where m = 2, d is the average number of R₂SiO₂ / ₂ groups per molecule, is 1 or more and 16 or less, and R is independently, in each occurrence, selected from hydrocarbyl groups having 1 to 8 carbon atoms, a silyl hydride functional siloxane; (c) a platinum-based hydrosilylation catalyst, and wherein there is at least 4 molar equivalents of silyl hydride functional groups relative to the allyl functional groups in the reaction composition. A reaction composition.

2. The reaction composition according to claim 1, wherein each R of the silyl hydride functional siloxane is methyl.

3. The reaction composition according to claim 1 or 2, further characterized in that the silyl hydride functional siloxane has d = 1 and each R is methyl.

4. The reaction composition according to any one of claims 1 to 3, wherein the concentration of the platinum-based hydrosilylation catalyst is 1 or more parts per million by weight based on the weight of the composition.

5. Steps: (a) providing a reaction composition according to any one of claims 1 to 4; and (b) heating the reaction composition to a temperature in the range of 80 to 250 °C for 1 hour or more. A process.

6. The process according to claim 5, wherein providing the reaction composition includes purifying the allyl polyether by exposing it to at least one component selected from the group consisting of alumina, zeolite, activated carbon, and silica alumina before and / or during the heating step (b).

7. The process according to claim 5 or 6, including removing unreacted silyl hydride functional polysiloxane after the heating step (b).

8. Steps (a) and (b) constitute a first hydrosilylation reaction to produce a first hydrosilylation product having a silyl hydride functionality, and the process further comprises, after heating step (b), adding an alkene-functional siloxane to the first hydrosilylation product and then heating to effect a second hydrosilylation reaction between the first hydrosilylation product and the alkene-functional siloxane in step (c). The process according to any one of claims 5 to 7.

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