Silicone-polyether copolymers and methods for their synthesis

Abstract

Silicone-polyether copolymers and methods for their preparation and use are provided. Since the silicone-polyether copolymers have a refractive index greater than 1.46, they are useful in a variety of applications, including hair care compositions.

Description

[Technical Field]

[0001] The present invention relates to silicone-polyether copolymers (SPE copolymers) and methods for their synthesis and use. [Background technology]

[0002] Silicone-polyether copolymers (SPE copolymers) are used in countless applications, including as wetting agents, thickeners, or surfactants. SPE copolymers are used in coatings and polyurethane foams. They are also used in personal care compositions, such as those described in Keil's U.S. Patent No. 4,265,878 and Rentsch's U.S. Patent No. 5,387,417. There is an industry need for lower-cost alternatives to phenyl-functionalized siloxanes for these applications. [Overview of the project]

[0003] Silicone-polyether copolymers (SPE copolymers) are provided. Methods for synthesizing SPE copolymers are also provided. [Modes for carrying out the invention]

[0004] The method for synthesizing the SPE copolymer described above involves 1) combining starting materials comprising A) an alkenyloxyaryl-terminated glycol ether, B) a polyorganohydrogensiloxane, and C) a catalyst for the hydrosilylation reaction, under conditions that induce a hydrosilylation reaction. The starting materials may optionally further include D) an alkenyl-functionalized aromatic compound different from A) the alkenyloxyaryl-terminated glycol ether, E) a dialkenyl-terminated siloxane oligomer, F) a solvent, or a combination of two or more of D), E), and F).

[0005] Step 1) can be carried out by any convenient means in any convenient apparatus. For example, when the method is carried out in batch mode, a reactor having heating and cooling means (such as a jacket containing water or other heat transfer fluid) and mixing means (such as a baffle and / or stirrer) may be used. One or more of the starting materials may be mixed in the reactor, and then the remaining starting materials may be added all at once, or continuously or intermittently aliquoted into the reactor. For example, starting materials having alkenyl groups, such as A) alkyloxyaryl-terminated glycol ethers, and, if used, D) alkenyl-functionalized aromatic compounds and / or E) dialkenyl-terminated siloxane oligomers, may be combined with B) polyorganohydrogensiloxane, and then all or part of C) hydrosilylation catalyst may be added. The alkenyl-functionalized starting material and the additional portion of the hydrosilylation reaction catalyst C) may be added one or more times until the silicon-bonded hydrogen atoms of B) polyorganohydrogensiloxane react with the alkenyl group.

[0006] Alternatively, alkenyl-containing starting materials, such as A) alkenyloxyaryl-terminated glycol ethers, and, if used, D) alkenyl-functionalized aromatic compounds, and / or E) dialkenyl-terminated siloxane oligomers, may be combined in the reaction group with all or part of C) the hydrosilylation catalyst. Subsequently, B) polyorganohydrogensiloxane may be added continuously or intermittently while heating or cooling to control the reaction rate. Although not theoretically binding, if the hydrosilylation reaction is carried out on a commercial scale, for safety reasons, it may be desirable to separate B) polyorganohydrogensiloxane and C) the hydrosilylation catalyst until immediately before the reaction with the alkenyl-functionalized starting material.

[0007] The hydrosilylation reaction in step 1) may be carried out at a temperature of 50°C to 150°C for a sufficient amount of time to react all of the silicon-bonded hydrogen atoms of starting material B) with the alkenyl groups of starting material A) (and, if present, starting material D) and / or starting material E)).

[0008] This method may optionally further include one or more additional steps. For example, one or more of the starting materials may be optionally dissolved in solvent F) before or during step 1). For example, the hydrosilylation catalyst C) may be dissolved or dispersed in solvent F) before being combined with other starting materials used in step 1). This method may optionally further include step 2) recovery of the SPE copolymer. Recovery may be carried out by any convenient means, for example, Color removal (for example, by treating the reaction product containing the SPE copolymer prepared in step 1 by passing the reaction product through a packed bed of activated carbon, either in a batch or continuous manner, using an adsorbent such as activated carbon), Filtration (for example, to remove activated carbon and / or other fine particles in a batch process), and / or This may be carried out by one or more of the following: stripping and / or distillation (for example, to remove a solvent if used, by-products of the hydrosilylation reaction if present, such as isomerization products, and / or excess unreacted starting materials (e.g., A) alkenyloxyaryl-terminated glycol ethers, as described below).

[0009] The starting material A) is an alkenyloxyaryl-terminated glycol ether, which has the general formula A1).

[0010] [ka] The formula has, where X is H or methyl, D has the empirical formula -C2H4- or -C3H6-, and the subscript n is 1, 2, or 3. Alternatively, X may be methyl. Alternatively, D may have a formula selected from -CH2-CH2- or -CH2-CH(CH3)-. Alternatively, the subscript n may be 1 or 2, or the subscript n may be 1. Alternatively, when X is H and D is -C2H4-, the subscript n may be 2 or 3. Alternatively, A) Alkenyloxyaryl-terminated glycol ethers are each R 3 When H, it may have the general formula A2).

[0011] [ka] In the formula, X, D, and the subscript n are as described and illustrated above. Examples of alkenyloxyaryl-terminated glycol ethers are shown in Table A below.

[0012] [Table 1-1]

[0013] [Table 1-2]

[0014] Alternatively, the alkenyloxyaryl-terminated glycol ether may be selected from the group consisting of (2-(allyloxy)propoxy)benzene, (2-(2-(allyloxy)ethoxy)ethoxy)benzene, (2-(2-(allyloxy)propoxy)propoxy)benzene, (2-((2-methylallyl)oxy)ethoxy)benzene, (2-((2-methylallyl)oxy)ethoxy)benzene, and (2-(2-((2-methylallyl)oxy)propoxy)propoxy)benzene.

[0015] Alkenyloxyaryl-terminated glycol ethers may be prepared by a process that includes combining starting materials containing alkylene glycol aryl ethers (such as alkylene glycol phenyl ethers), a catalyst (such as an organic ammonium halide), and an alkenyl halide such as allyl chloride under conditions that induce the reaction. An aqueous solution of a base, such as an aqueous sodium hydroxide solution, may be added while mixing and optionally while heating. The resulting slurry may be separated, for example, using a separatory funnel. The organic phase may be further purified while heating and optionally under reduced pressure, for example, by washing with water, separation, and stripping and / or distillation, to recover the alkenyloxyaryl-terminated glycol ethers. For example, (2-(allyloxy)ethoxy)benzene (2-allyloxyethylphenyl ether) can be prepared as described in U.S. Patent No. 5,466,845, Example 2a), and alkenyloxyaryl-terminated glycol ethers can be prepared as described in the following examples, or as described in U.S. Patent No. 5,466,845, by changing the appropriate starting materials.

[0016] A) The following raw materials for preparing alkenyloxyaryl-terminated glycol ethers are available from The Dow Chemical Company in Midland, Michigan, USA. Ethylene glycol phenyl ether having the formula C6H5-O-CH2-CH2-OH is available as DOWANOL® EPh Glycol Ether. Propylene glycol phenyl ether having the formula C6H5-O-CH2-CH(CH3)-OH is available as DOWANOL® PPh Glycol Ether. Diethylene glycol phenyl ether having the formula C6H5-O-CH2CH2-O-CH2CH2-OH is available as DOWANOL® DiEPh Glycol Ether. Dipropylene glycol phenyl ether having the formula C6H5-O-CH2-CH(CH3)-O-CH2-CH(CH3)-OH is available as DOWANOL® DiPPh Glycol Ether.

[0017] A) The amount of alkenyloxyaryl-terminated glycol ether depends on various factors, including the silicon-bonded hydrogen content of B) organohydrogensiloxane and the presence of either or both of D) alkenyl-functional aromatic hydrocarbons or E) dialkenyl-terminated siloxane oligomers. However, the amount of A) alkenyloxyaryl-terminated glycol ether is sufficient to provide at least one silicon-bonded group of formula A1') per molecule of the SPE copolymer. Alternatively, the amount of A) alkenyloxyaryl-terminated glycol ether may be sufficient to ensure that the molar ratio of alkenyloxy groups in starting material (A) to silicon-bonded hydrogen atoms in starting material (B) is >0 / 1 to 1.15, or 1.1 / 1 to 1.15 / 1. Alternatively, the amount of starting material A) may be sufficient to react all of the silicon-bonded hydrogen atoms in starting material B), resulting in the SPE copolymer containing no unreacted silicon-bonded hydrogen atoms. Alternatively, when starting materials D) and E) are present, the total amount of starting materials A), D), and E) may be sufficient to react all of the silicon-bonded hydrogen atoms in starting material B), and as a result, the SPE copolymer will not contain any unreacted silicon-bonded hydrogen atoms.

[0018] Although not bound by theory, in the above equations A1) and A2), when the subscript n ≤ 3, the alkenyloxyaryl-terminated glycol ether is readily distilled, resulting in a clean intermediate for the hydrosilylation reaction. However, when n > 3, residual catalyst and unreacted starting materials may be present in the product due to the high boiling points of these substances, which could impair the possibility of recovering the alkenyloxyaryl-terminated glycol ether, for example, by distilling the reaction product.

[0019] In the above method, the starting material B) is given by the unit formula (B1): (R 1 3SiO 1 / 2 ) a (R 1 2SiO2 / 2 ) b (R 1 HSiO 2 / 2 ) c (R 1 2HSiO 1 / 2 ) d (R 1 SiO 3 / 2 ) e (HSiO 3 / 2 ) f (SiO 4 / 2 )<0(000020>is a polyorganohydrogensiloxane containing, where the subscripts a, b, c, d, e, f, and g represent the average number of each unit in the formula, a≥0, d≥0, the amount (a + d)≥2, b≥0, c≥1, e≥0, f≥0, the amount (c + d + f)≥1, g≥0, and the amount (a + b + c + e + f + g)=2 to 10,000, and each R 1 is an alkyl group having 1 to 12 carbon atoms. The alkyl group of R 1 is exemplified by methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, isobutyl, sec-butyl, and t-butyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and branched-chain alkyl groups having 5 to 12 carbon atoms, and cyclic alkyl groups such as cyclopentyl and cyclohexyl. Alternatively, each R 1 may be a methyl group.

[0020] Alternatively, the polyorganohydrogensiloxane may be linear. The linear polyorganohydrogensiloxane may contain the unit formula (B2): (R 1 3SiO 1 / 2 ) a (R 1 [[ID=]](R 2SiO 2 / 2 ) b (R 1 HSiO 2 / 2 ) [[ID=]](R c (R 1 2HSiO 2 / 2 ) d where R 1As described above, a is 0, 1, or 2, d is 0, 1, or 2, quantity (a+d)=2, quantity (c+d)≧1, and b and c are as described above. Alternatively, in formula (B2), the subscripts b and c may have values ​​such that 3≦b≦100, 3≦c≦100, quantity (b+c)≦150, or 6≦(b+c)≦150. Alternatively, polyorganohydrogensiloxane has the unit formula (B3):(R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 HSiO 2 / 2 ) c It may include, in the formula, R 1 As stated above, a=2, b≧0, c≧1. Alternatively, in equation (B3), the subscripts b and c may have values ​​such that 3.4≦b 57, 3.3≦c 50, and quantity (b+c)≦101, or 6.7≦(b+c)≦101. Alternatively, in equation (B2) and / or equation (B3), the subscripts b and c may have values ​​such that 20≦b≦60, 20≦c≦50, and 40≦(b+c)≦110.

[0021] The silicon-bonded hydrogen (Si-H) content of polyorganohydrogensiloxanes can be determined using quantitative infrared analysis in accordance with ASTM E168.

[0022] The ratio of silicon-bonded hydrogen to alkenyl (vinyl) is frequently used to determine the amount of starting material when the reaction depends on hydrosilylation. Generally, this is determined by calculating the total weight % of alkenyl groups in the starting material, e.g., vinyl[V], and the total weight % of silicon-bonded hydrogen[H] in the starting material. If the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, then the molar ratio of silicon-bonded hydrogen to vinyl is 27[H] / [V].

[0023] The polyorganohydrogensiloxanes suitable for use in this specification are: (i) α,ω-trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (ii) α,ω-trimethylsiloxy-terminated polymethylhydrogensiloxane, (iii) α,ω-dimethylhydrogensiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), (iv) α,ω-dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane, and (v) A combination of two or more of these, as exemplified by

[0024] Furthermore, linear polyorganohydrogensiloxanes are commercially available, for example, those available from Gelest, Inc. (Morrisville, Pennsylvania, USA), such as HMS-H271, HMS-071, HMS-993, HMS-301, HMS-031, HMS-991, HMS-992, HMS-993, HMS-082, HMS-151, HMS-013, HMS-053, HAM-301, and HMS-HM271. Methods for preparing polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified by U.S. Patent No. 2,823,218 by Speier, et al., U.S. Patent No. 3,957,713 by Jeram et al., U.S. Patent No. 4,329,273 by Hardman, et al., U.S. Patent No. 4,370,358 by Hayes, et al., U.S. Patent No. 4,707,531 by Shirahata, and U.S. Patent No. 5,310,843 by Morita.

[0025] The starting material C) is a hydrosilylation catalyst. This catalyst facilitates the reaction between the alkenyl group in A) alkenyloxyaryl-terminated glycol ethers (and D, if present), alkenyl-functional aromatic compounds, and / or E) dialkenyl-terminated siloxane oligomers) and the silicon-bonded hydrogen atoms in B) polyorganohydrogensiloxane. The catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation catalyst may be a platinum group metal or a compound or complex of a platinum group metal. For example, the hydrosilylation catalyst may be a rhodium diphosphine chelate such as chloride tris(triphenylphosphane)rhodium(I) (Wilkinson catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an alkenyl-functional organopolysiloxane, such as a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum (Karstedt catalyst), or a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby catalyst). Alternatively, the compound or complex may be microencapsulated in a matrix or core-shell structure. Hydrosilylation catalysts are known in the art, for example, as described in PCT application publication WO2021 / 081822 and the references cited therein. Hydrosilylation catalysts are commercially available, for example, SYL-OFF® 4000 Catalyst and SYL-OFF® 2700, which are available from Dow Silicones Corporation in Midland, Michigan, USA.

[0026] C) The amount of the hydrosilylation catalyst is sufficient to catalyze the hydrosilylation reaction between the alkenyl group in starting material A) (and starting material D, an aromatic compound, if present) and the silicon-bonded hydrogen atoms of B) the polyorganohydrogensiloxane. C) The amount of the hydrosilylation catalyst may be sufficient to provide 1 ppm to 1,000 ppm of platinum group metals based on the total weight of starting materials A), B), C) (and D) and / or E) used in this method. Alternatively, C) the amount of the hydrosilylation catalyst may be sufficient to provide 2 ppm to 50 ppm or 2 ppm to 10 ppm of platinum group metals based on the same criteria.

[0027] Starting material D) is an alkenyl-functional aromatic compound that may be optionally added during the process for synthesizing the SPE copolymer. Starting material D) is different from starting material A). Starting material D) may have formula D1).

[0028] [ka] In the formula, each R is independently selected from the group consisting of H, a halogen atom, OH, methyl, and methoxy, D' is a covalent bond, a group of formula -CH2-, or a group of formula -CH2-O-, and R'' is H or methyl. Alternatively, each R may be either H or methyl. Alternatively, each R may be H.

[0029] Alternatively, the starting material D) may have formula D2).

[0030] [ka] In the formula, D' and R'' are as described and illustrated above.

[0031] For example, D) the alkenyl-functional aromatic compound may be selected from the group consisting of styrene, α-methylstyrene, eugenol, allylbenzene, allylphenyl ether, 2-allylphenol, 2-chlorostyrene, 4-chlorostyrene, 4-methylstyrene, 3-methylstyrene, 4-t-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, and 2,4,6-trimethylstyrene. Alternatively, the starting material D) may be, for example, alpha-methylstyrene, commercially available from Sigma Aldrich, Inc. of St. Louis, Missouri, USA. Those skilled in the art will recognize that the starting material D) may optionally contain a free radical polymerization inhibitor.

[0032] Starting material D) is optional and therefore may not be present, i.e., its usage may be 0. Alternatively, if starting material D) alkenyl-functional aromatic compound is present, the amount of D) alkenyl-functional aromatic compound may be sufficient to ensure that the molar ratio of alkenyl groups from starting material D) to silicon-bonded hydrogen atoms of starting material B) is >0 / 1 to 0.98 / 1.

[0033] The starting material E) is given by the formula

[0034] [ka] An optional dialkenyl-terminated siloxane oligomer, in which R 1 As described above, each R 5 R is an independently selected alkenyl group consisting of 2 to 6 carbon atoms, where the subscript m is 0 or 1. Alternatively, each R 5 The compound may be independently selected from vinyl, allyl, or hexenyl. Alternatively, the subscript m may be 0. Examples of suitable oligomers include divinyltetramethyldisiloxane (M Vi M Vi This includes, and is available from Dow.

[0035] Starting material E) is optional. The amount of starting material E) may be sufficient to ensure that the molar ratio of alkenyl groups from starting material E) to silicon-bonded hydrogen atoms of starting material B) is ≥ 0 / 1 to 0.1 / 1, or ≥ 0.001 / 1 to 0.002 / 1. Alternatively, starting material E) may be omitted.

[0036] The starting material F) is an optional solvent. The solvent may be added to facilitate the introduction of certain starting materials, such as C) a hydrosilylation catalyst. The solvents that can be used herein are those that help to fluidize the starting materials but do not react with them in nature. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility means that the solvent is sufficient to dissolve and / or disperse the starting materials.

[0037] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as DOWSIL® 200 Fluid and DOWSIL® OS Fluid, which are commercially available from Dow and have a molecular weight of 0.5 to 1.5 cSt.

[0038] Alternatively, the solvent may include organic solvents. Organic solvents may include alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, or xylene; aliphatic hydrocarbons such as heptane, hexane, or octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; white spirit; mineral spirit; naphtha; n-methylpyrrolidone; or combinations thereof.

[0039] The amount of solvent depends on various factors, including the type of solvent selected and the amount and type of other starting materials selected for use in this method. However, the amount of solvent may be in the range of 1% to 99% or 2% to 90% based on the total weight of all starting materials in step 1). All or part of the solvent may be optionally removed during and / or thereafter in step 1).

[0040] SPE copolymers can be prepared by the method described above, and will be described in more detail below. Silicone-polyether copolymers (SPE copolymers) are represented by the unit formula (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 1 2R 2 SiO 1 / 2 ) d (R 1 SiO3 / 2 ) e (R 2 SiO 3 / 2 ) f (SiO 4 / 2 ) g The formula includes the subscripts a, b, c, d, e, f, and g, as well as R 1 This is as described above. In the unit formula, each R 2 These are independently selected from the group consisting of H, formula E1'), formula D1'), and formula A1'), Equation E1') is,

[0041] [ka] And in the formula, R 1 And the subscript m is as described above, and each R 6 It is a divalent hydrocarbon group, Equation D1') is,

[0042] [ka] And in the formula, R, D', and R'' are as described above. Equation A1') is,

[0043] [ka] In the formula, X, D, R 3 , and the subscript n are as described above, except that at least one R per molecule 2 This is conditional on having formula A1'). Those skilled in the art will recognize that formula E1') is a group derived from E) an alkenyl-terminated siloxane oligomer, formula D1') is a group derived from D) an alkenyl-functionalized aromatic compound, and formula A1') is derived from A) an alkenyloxyaryl-terminated glycol ether, each as described above and used in methods for synthesizing SPE copolymers. Those skilled in the art will recognize that the alkenyl group (R) of the starting material E1) 5When ) undergoes a hydrosilylation reaction with the silicon-bonded hydrogen atoms of the starting material B), branching is created between molecular sites of the B) polyorganohydrogensiloxane and / or between different molecules of the polyorganohydrogensiloxane, further recognizing that both ends of the group of formula E1') bond to the silicon-bonded hydrogen atoms from the B) polyorganohydrogensiloxane. The branching may be imparted to the SPE copolymer by formula E1').

[0044] Alternatively, each R may be H, and equation D1') becomes equation D2')

[0045] [ka] This may also be the case, where R'' and D' are as described above.

[0046] Alternatively, each R 3 (A1') may be hydrogen, and (A2')

[0047] [ka] This may also be the case, where X, D, and the subscript n are as described above.

[0048] The properties of the resulting SPE copolymer may be controlled, for example, by changing the selection of B) polyorganohydrogensiloxane with varying amounts of silicon-bonded hydrogen atoms, and by changing the amounts of starting material A), and, if present, starting materials D) and / or E). However, this method may be used to produce an SPE copolymer having one or more of the following properties: R per molecule 2 All cases from 0 mol% to 95 mol% may have formula D1'), or R per molecule 2 All cases >0 mol% to 95 mol% may have formula D1'). Alternatively, R per molecule 2The remainder up to 100 mol% of all cases may have formula A1'). Alternatively, R 2 Each of the examples may have formula A1'). Alternatively, R per molecule 2 All cases from 0 mol% to 95 mol% may have formula D2'), or R per molecule 2 All cases >0 mol% to 95 mol% may have formula D2'). Alternatively, R per molecule 2 The remainder up to 100 mol% of all cases may have formula A2'). Alternatively, R 2 Each of these cases may have the formula A2').

[0049] How to use The above-described SPE copolymers can be used in countless applications. For example, SPE copolymers may be used as surfactants or additives for polyurethane foams. Alternatively, SPE copolymers may be used as coating additives. Alternatively, SPE copolymers may be used as additives such as adhesion promoters for silicone pressure-sensitive adhesive compositions. Alternatively, SPE copolymers may be used in addition to or instead of the silicone polyethers disclosed in personal care compositions, such as those described in U.S. Patent No. 4,265,878 of Keil and U.S. Patent No. 5,387,417 of Rentsch. Alternatively, SPE copolymers may be used as a substitute for more expensive phenylmethyl silicones in applications where a high refractive index is desired. These high-RI applications may include hair care compositions. [Examples]

[0050] The following examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are defined in Table 1 below.

[0051] [Table 2-1]

[0052] Table 2-2

[0053] In this Example 1, (2-(allyloxy)ethoxy)benzene was prepared as follows: A 3 L round-bottom flask equipped with an overhead stirrer, a water-cooled condenser, an addition funnel, and a nitrogen bubbler was placed in a temperature-controlled heated mantle and filled with 804.6 g (5.82 mol) DOWANOL® EPh, 19.39 g of Aliquat® 336, and 621.65 g (8.12 mol) of allyl chloride. The clear yellow solution was stirred with a Teflon® paddle and 833.1 g (10.4 mol) of 50% aqueous sodium hydroxide solution was added dropwise over approximately 1 hour. During the addition process, the internal temperature rose from 21°C to 50°C. A smooth white slurry was formed. The mixture was heated to 65–70°C. GC analysis of the upper organic phase after 3 hours revealed that it contained 6.0 area% allyl chloride, 0.43 area% DOWANOL® EPh, and 90.3 area% EPh allyl ether. After cooling to ambient temperature, the white slurry was diluted with 665.5 g of water, and the mixture was transferred to a 3 L separatory funnel to remove the lower aqueous phase (1666.4 g) containing some heavy white solid precipitate. The organic phase was washed with 205.3 g of water to remove the lower aqueous phase (245.6 g). The organic phase (1173.1 g) was mixed with 14.0 g of MagSil, and the slurry was vacuum filtered through filter paper to obtain 1137.7 g of clear yellow filtrate. The filtrate was packed into a 2 L round-bottom flask equipped with a 6-inch high vacuum-jacketed silver-plated Vigreux column with a magnetic stirrer and a water-cooled distillate condenser. A temperature-controlled heating mantle was attached to the flask, and a vacuum was applied using an Edwards vacuum pump protected with dry ice. The pre-distillate (10.41 g) was collected at a head temperature of 100 °C, a pot temperature of 112 °C, and a pressure of 1.9 Torre. The product fraction was collected in a 2 L receiving flask at a head temperature of 98–105 °C, a pot temperature of 110–117 °C, and a pressure of 1.5–2 Torre until no further distillate could be collected. GC analysis yielded 984.4 g (5.52 mol, 94.9% yield) of (2-allyloxy)ethoxybenzene (2-allyloxyethylphenyl ether, CAS number 93066-80-9) with a purity of >99 area%.

[0054] In this Example 2, (2-(allyloxy)propoxy)benzene was prepared as follows: A 3 L round-bottom flask equipped with an overhead stirrer, water-cooled condenser, addition funnel, and nitrogen bubbler was placed in a temperature-controlled heating mantle and filled with 872.2 g (5.73 mol) DOWANOL® PPh, 22.43 g Aliquat® 336, and 604.4 g (7.90 mol) allyl chloride. GC analysis revealed that the allyl chloride content was 33.2 area%, and the DOWANOL® PPh content was 62.0 area%. The clear yellow solution was stirred with a Teflon® paddle, and 820.7 g (10.3 mol) of 50% aqueous sodium hydroxide solution was added dropwise over approximately 1 hour. During the addition process, the internal temperature rose to 21°C to 37°C, and a white slurry was formed. The mixture was stirred and gently heated to 50–60°C. The highest temperature reached was 70°C. Two hours after adding the base, GC analysis of the upper organic phase revealed that allyl chloride accounted for 23.4 area%, DOWANOL® PPh for 37.9 area%, and PPh allyl ether for 36.4 area%. An additional 6.4g of Aliquat® 336 was added. GC analysis of the upper organic phase after stirring overnight at 55°C revealed that allyl chloride accounted for 4.1 area%, DOWANOL® PPh for 3.8 area%, and PPh allyl ether for 85.0 area%. An additional 2.47g of Aliquat® 336 was added. GC analysis after three hours at 55°C showed no further transformation. Heating to 70-75°C did not improve the transformation. After cooling to ambient temperature, the white slurry was diluted with 826.3 g of water, and the mixture was transferred to a 3 L separatory funnel to remove the lower aqueous phase (1830.9 g) containing some heavy white solid precipitate. The organic phase (1220.3 g) was mixed with 34.1 g of MagSil, and the slurry was vacuum filtered through filter paper to obtain 1140.1 g of clear yellow filtrate. The filtrate was packed into a 2 L round-bottom flask equipped with a 6-inch high silver-plated Vigreux column with a vacuum jacket, a magnetic stirrer, and a water-cooled distillate condenser. A temperature-controlled heating mantle was attached to the flask, and vacuum was applied using an Edwards vacuum pump protected with dry ice.The pre-distillate (92.55 g, 93.8 area% PPh allyl ether as determined by GC analysis) was collected at a head temperature of 40–100°C, a pot temperature of 100–115°C, and a pressure of 2.5 Torre. The product fraction was collected in a 2 L receiving flask at a head temperature of 96–98°C, a pot temperature of 105–110°C, and a pressure of 2–2.5 Torre until no further distillate could be collected. GC analysis revealed a purity of 96.6 area% (3.3 area% DOWANOL® PPh) and yielded 904.0 g (4.70 mol, 82.0% yield) of (2-(allyloxy)propoxy)benzene.

[0055] In this Example 3, 2-(2-allyloxy)ethoxy)ethoxy)benzene was prepared as follows: A 2 L round-bottom flask equipped with an overhead stirrer, a water-cooled condenser, an addition funnel, and a nitrogen bubbler was placed in a temperature-controlled heated mantle and filled with 403.92 g of phenyl glycol ether (approximately 70% DOWANOL® DiEPh, 15% DOWANOL® EPh), 8.15 g of Aliquat® 336, and 265.54 g of allyl chloride. GC analysis revealed that the allyl chloride was 34.2 area%, DOWANOL® EPh was 12.9 area%, and DOWANOL® DiEPh was 52.9 area. The clear yellow solution was stirred with a Teflon® paddle and heated to 50°C, and 408 g of 50% aqueous sodium hydroxide solution was added dropwise. During the addition process, the temperature rose to 60°C. A smooth white slurry was formed. The mixture was heated to 60-70°C. GC analysis of the upper organic phase after 3 hours revealed 5.9 area% allyl chloride, 17.4 area% EPh allyl ether, 19.4 area% unreacted DOWANOL® DiEPh, and 62.9 area% DiEPh allyl ether. GC analysis of the upper organic phase after overnight stirring revealed 0.67 area% allyl chloride, 18.0 area% EPh allyl ether, 0.94 area% unreacted DOWANOL® DiEPh, and 65.4 area% DiEPh allyl ether. After cooling to ambient temperature, the white slurry was diluted with 400 mL of water, and the mixture was transferred to a 3 L separatory funnel. The lower aqueous phase (874.4 g), containing some heavy white solid precipitate, was removed. The organic phase was washed with 100 mL of water, and 112.0 g of the aqueous phase was removed. The organic phase (541.36 g) was mixed with 25.8 g of anhydrous magnesium sulfate, and the slurry was vacuum filtered through filter paper to obtain 492.93 g of clear yellow filtrate. The filtrate was packed into a 1 L round-bottom flask equipped with a magnetic stirrer and a short-path distillation head with a water-cooled distillate condenser. A temperature-controlled heating mantle was attached to the flask, and vacuum was applied using an Edwards vacuum pump protected with dry ice.The product fraction was collected in a 1 L receiving flask at a head temperature of 115–127°C, a pot temperature of 133–135°C, and a pressure of 1.3–4.4 Torre until no further distillate could be collected, yielding 429.91 g (88% yield assuming 100% pure DiEPh) of (2-(2-allyloxy)ethoxy)ethoxy)benzene (20.3 area% EPh allyl ether, 71.2 area% DiEPh allyl ether, as determined by GC analysis).

[0056] In this Example 4, (2-(2-allyloxy)propoxy)propoxy)benzene was prepared as follows: A 2 L round-bottom flask equipped with an overhead stirrer, a water-cooled condenser, an addition funnel, and a nitrogen bubbler was placed in a temperature-controlled heated mantle and filled with 429.91 g of phenyl glycol ether (95% DiPPh, 5% DOWANOL® PPh, 8.92 g of Aliquat® 336, and 243.0 g of allyl chloride). GC analysis revealed that It was found that allyl chloride was present at 28.8 area%, DOWANOL® PPh at 3.4 area%, and DiPPh at 62.3 area%. The clear yellow solution was stirred with a Teflon® paddle, and 372.0 g of 50% sodium hydroxide aqueous solution was added dropwise over 17 minutes. The temperature rose to 25°C to 34°C. A smooth white slurry was formed. The mixture was heated to 60-70°C. GC analysis of the upper organic phase after 3 hours revealed that allyl chloride was present at 5.7 area%, and PPh allyl ether was present. It was found that the initial composition was 4.7 area%, DiPPh was 10.3 area%, and DiPPh allyl ether was 68.2 area%. GC analysis of the upper organic phase after overnight stirring revealed that it consisted of 1.9 area% allyl chloride, 4.7 area% PPh allyl ether, 7.6 area% DiPPh, and 73.6 area% DiPPh allyl ether. After cooling to ambient temperature, the white slurry was diluted with 532.58 g of water, the mixture was transferred to a 3 L separatory funnel, and the clear lower aqueous phase (984.6 g) was removed. The organic phase was washed with 159.31 g of water to remove 151.9 g of aqueous phase. The organic phase (666.88 g) was mixed with 39.52 g of anhydrous magnesium sulfate, and the slurry was vacuum filtered through filter paper to obtain 522.54 g of clear yellow filtrate. The filtrate was packed into a 1 L round-bottom flask equipped with a magnetic stirrer and a short-path distillation head with a water-cooled distillate condenser. A temperature-controlled heating mantle was attached, and vacuum was applied using an Edwards vacuum pump protected with dry ice.The product fraction was collected in a 1 L receiving flask at a head temperature of 110–122°C, a pot temperature of 130–135°C, and a pressure of 1 Torr until no further distillate could be collected, yielding 479.83 g (94% yield assuming 100% pure DiPPh) of (2-(2-allyloxy)propoxy)propoxy)benzene (7.2 area% PPh allyl ether, 79.5 area% DiPPh allyl ether, as determined by GC analysis).

[0057] In this Example 5, (2-((2-methylallyl)oxy)ethoxy)benzene was prepared as follows: A 3 L round-bottom flask equipped with an overhead stirrer, a water-cooled condenser, an addition funnel, and a nitrogen bubbler was placed in a temperature-controlled heated mantle and filled with 800.8 g (5.79 mol) DOWANOL® EPh, 13.42 g of Aliquat® 336, and 737.5 g (8.14 mol) of 3-chloro-2-methyl-1-propene. GC analysis revealed that 3-chloro-2-methyl-1-propene was present at 43.7 area%, and DOWANOL® EPh was present at 56.0 area%. The clear yellow solution was stirred with a Teflon® paddle, and 863.0 g (10.8 mol) of a 50% sodium hydroxide aqueous solution was added dropwise over approximately 1 hour. During the addition process, the internal temperature rose from 18°C ​​to 36°C. A white slurry was formed. The mixture was heated to 60°C and stirred overnight. GC analysis of the upper organic phase revealed 10.3 area% of 3-chloro-2-methyl-1-propene, 0.64 area% of DOWANOL® EPh, and 87.6 area% of EPh metharyl ether. The white slurry was diluted with 549.5 g of water, and the mixture was transferred to a 3 L separatory funnel. The lower aqueous phase (1581.5 g), containing some heavy white solid precipitate, was removed at 40°C. The organic phase (1298.7 g) was mixed with 27.65 g of MagSil, and the slurry was vacuum filtered through filter paper to obtain 1234.2 g of clear yellow filtrate. The filtrate was packed into a 2 L round-bottom flask equipped with a 6-inch high vacuum-jacketed silver-plated Vigreux column with a magnetic stirrer and a water-cooled distillate condenser. A temperature-controlled heating mantle was attached, and a vacuum was applied using an Edwards vacuum pump protected with dry ice. The pre-distillate (29.45 g) was collected at a head temperature of 99–117°C, a pot temperature of up to 127°C, and a pressure of 4.5 Torre. The product fraction was collected in a 2 L receiving flask at a head temperature of 116–117°C, a pot temperature of 120–127°C, and a pressure of 3.9–4.1 Torre until no further distillate could be collected. GC analysis yielded 1010.6 g (5.26 mol, 90.7% yield) of (2-(2-methylallyl)oxy)ethoxybenzene with a purity of 99.6 area%.

[0058] In this Example 6, (2-((2-methylallyl)oxy)propoxy)benzene was prepared as follows: A 3 L round-bottom flask equipped with an overhead stirrer, a water-cooled condenser, an addition funnel, and a nitrogen bubbler was placed in a temperature-controlled heated mantle and packed with 828.5 g (5.44 mol) DOWANOL® PPh and 672.2 g (7.42 mol) 3-chloro-2-methyl-1-propene. GC analysis revealed that 3-chloro-2-methyl-1-propene was present at 40.0 area%, and DOWANOL® PPh was present at 60.0 area%. The clear solution was stirred with a Teflon® paddle, packed with 20.00 g of Aliquat® 336, heated to 44°C, and 808.2 g (10.1 mol) of 50% aqueous sodium hydroxide solution was added dropwise over approximately 1.5 hours. During the addition process, the temperature rose to 49°C, and the heating mantle was removed to control the temperature. A white slurry was formed. The mixture was stirred at 50-60°C. Two hours after the base was added, GC analysis of the upper organic phase revealed that it contained 25.4 area% 3-chloro-2-methyl-1-propene, 31.7 area% DOWANOL® PPh, and 40.9 area% PPh allyl ether. GC analysis of the upper organic phase after stirring overnight at 50°C revealed that it contained 9.0 area% 3-chloro-2-methyl-1-propene, 8.7 area% DOWANOL® PPh, and 78.7 area% PPh metharyl ether. An additional 12.44 g of Aliquat® 336 and 99.9 g of 50% aqueous sodium hydroxide solution were added. GC analysis of the upper organic phase after stirring overnight at 50°C revealed that it contained 4.2 area% 3-chloro-2-methyl-1-propene, 2.7 area% DOWANOL® PPh, and 87.6 area% PPh metharyl ether. After cooling to ambient temperature, the white slurry was diluted with 863.6 g of water, and the mixture was transferred to a 3 L separatory funnel to remove the lower aqueous phase (1946.2 g) which contained some heavy white solid precipitate. The organic phase (1261.6 g) was mixed with 44.4 g of MagSil, and the slurry was vacuum filtered through filter paper to obtain 1180.6 g of clear yellow filtrate.The filtrate was charged into a 2 L round-bottom flask equipped with a 6-inch tall silver-plated Vigreux column with a magnetic stirrer and a water-cooled distillate condenser and a vacuum jacket. A temperature-controlled heating mantle was attached to the flask, and a vacuum was applied using an Edwards vacuum pump protected with dry ice. The fore-fraction (27.87 g, 21.6 area % PPh methallyl ether by GC analysis) was collected at a head temperature of 91 - 100 °C, a pot temperature of 97 - 111 °C, and 7 - 1.9 torr. The product fraction was collected in a 2 L receiving flask at a head temperature of 102 - 105 °C, a pot temperature of 119 - 142 °C, and a pressure of 1.7 - 2.1 torr until no more distillate could be collected, yielding 1044.6 g (5.06 mol, 93.1% yield) of (2-((2-methallyl)oxy)propoxy)benzene with a purity of 97.3 area % (2.7 area % DOWANOL™ PPh) by GC analysis.

[0059] In this Example 7, the SPE copolymer sample SPE-Ph1 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-neck round-bottom flask equipped with a digital overhead stirrer, a thermocouple, a stopper, a condenser, and a nitrogen inlet. The system was heated by a heating mantle equipped with a J-KEM temperature controller. In the pot were charged A-1) EPh allyl ether (9.08 g, the first portion, about 20%) prepared as described above in Example 1, and B-1) M2D 8.7 D H 3.7(54.6g) was added. The mixture was heated to 70°C under nitrogen. C-2) Pt catalyst solution (0.063mL) was added. This reaction is exothermic, and the temperature rose to 73.4°C. The second portion of EPh allyl ether (9.07g) was added. Additional Pt catalyst solution (5ppm, 0.063mL) was added. The temperature rose to 77.1°C. When the temperature dropped to 70°C, the third portion of EPh allyl ether (18.15g) was added along with additional Pt catalyst solution (5ppm, 0.063mL). The temperature rose to 74.5°C. When the temperature of the reaction mixture dropped to 72.5°C, the last portion of EPh allyl ether (9.10g) was added. The J-KEM temperature controller was set to 75°C for the remainder of the reaction time. After 2.5 hours, IR (2150cm²) was set. -1 A sample was taken for (0.5428 g in 2.3798 g of tetrachloroethylene): residual Si-H = 128.4 ppm. An additional Pt catalyst solution (5 ppm, 0.063 mL) was added over 2.75 hours. At 5 hours, IR (2150 cm) -1 A sample was taken for (0.5231 g in 2.3295 g of tetrachloroethylene): residual Si-H = N / D ppm. The reaction was stopped. After cooling to room temperature, the obtained substance was removed from the flask. The obtained liquid product (97.33 g, 27580-3) was stored in a plastic bottle. The Pt catalyst solution used in this reaction was sufficient to provide a total of 20 ppm of Pt. In this reaction, a molar excess of EPh allyl ether was used, and the molar ratio of allyl to Si-H was approximately 1.3. This crude substance (80.30 g) was subjected to distillation (Kugelrohr, 5.3 × 10⁻⁶). -2 The recovery amount was 78.55 g (mBar, 5 hours, 80-85°C). Based on the mass balance, not much light material (excess allyl or isomerized allyl) was removed.

[0060] In this Example 8, the SPE copolymer sample SPE-Ph2 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-neck round-bottom flask equipped with a digital overhead stirrer, a thermocouple, a stopper, a condenser, and a nitrogen inlet. The system was heated by a heating mantle equipped with a J-KEM temperature controller. To the pot were added A-3) DiEPh allyl ether (12.77 g, the first portion, about 25%) prepared as described above in Example 3, and B-1) M2D 8.7 D H 3.7 (49.14 g). The mixture was heated to 70 °C under nitrogen. The Pt catalyst solution (0.063 mL) was added. This reaction was exothermic and the temperature rose to 74.6 °C. When the temperature dropped to 72.0 °C, the second portion of DiEPh allyl ether (25.49 g) was added. An additional Pt catalyst solution (0.063 mL) was added. The temperature rose to 75.5 °C. When the temperature dropped to 73.7 °C, the last portion of DiEPh allyl ether (12.80 g) was added. The J-KEM temperature controller was set to 75 °C for the remaining reaction time. At 3 hours, a sample (A) was taken for IR (2150 cm -1 ): (0.5043 g in 2.3949 g of tetrachloroethylene): residual Si-H = 502 ppm. An additional Pt catalyst solution (0.063 mL) was added over 3 hours. At 5 hours, a sample (B) was taken for IR (2150 cm -1 ): (0.5722 g in 2.3899 g of tetrachloroethylene): residual Si-H = N / D ppm. The reaction was stopped. The resulting molten polymer was removed from the reactor when cooled to room temperature. The resulting liquid product (97.31 g) was stored in a plastic bottle. The catalyst used in this reaction was sufficient to provide a total of 15 ppm of Pt. In this reaction, an excess of A-3) DiEPPh allyl ether was used and the molar ratio of allyl to Si-H was about 1.3.

[0061] In this Example 9, the SPE copolymer sample SPE-Ph3 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a digital overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated by a heating mantle equipped with a J-KEM temperature controller. In the pot, A-4) DiPPh allyl ether (26.95 g, first portion, about 50%) prepared as described above in Example 4, and B-1) M2D 8.7 D H 3.7 (46.10g) was added. The mixture was heated to 70°C under nitrogen. C-2) Pt catalyst solution (0.063mL) was added. This reaction was not very exothermic, and the temperature rose to 69.5°C to 71.2°C. When the temperature dropped to 70.9°C, the remaining DiPPh allyl ether (26.97g) was added. Additional Pt catalyst solution (0.126mL) was added. The temperature rose to 74.4°C. The J-KEM temperature controller was set to 75°C for the remainder of the reaction time. After 2 hours, IR (2150cm²) -1 A sample was taken for (0.88 g in 3.58 g of tetrachloroethylene): residual Si-H = N / D ppm. The reaction was stopped. After cooling to room temperature, the resulting substance was removed from the flask. The liquid product (97.79 g, 27580-7) was stored in a plastic bottle. The catalyst used in this reaction was sufficient to provide a total of 15 ppm of Pt. In this reaction, excess DiPPh allyl ether was used, and the molar ratio of allyl to Si-H was approximately 1.3.

[0062] In this Example 10, the SPE copolymer sample SPE-Ph4 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a digital overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a J-KEM temperature controller. DiPPh allyl ether (26.95 g) prepared as described above in Example 4 was added to the pot, and B-1)M2D 8.7 D H 3.7(46.11g) was mixed and heated to 70°C. Pt catalyst solution (0.126mL) was added. This reaction is exothermic, and the temperature rose to 106°C in 10-15 minutes. The heating mantle was temporarily removed. When the temperature of the reaction mixture dropped to 92°C, heating was resumed and set to 70°C. After 1.5 hours, IR (2150cm²) -1 Sample (A) was taken for (0.38 g in 4.76 g of tetrachloroethylene): residual Si-H = 1047 ppm, which indicates Si-H = 76.49 mmol (Si-H conversion was 53.8% at this point). Approximately 46% of Si-H was ready to react with A-3) DiEPh allyl ether. After 2.25 hours, DiEPh ether (24.01 g) prepared as described above in Example 3 and an additional Pt catalyst solution (0.063 mL) were added. The reaction was not as exothermic as the previous step. The temperature rose to 69.1°C to 71.2°C. The J-KEM temperature controller was set to 75°C for the remainder of the reaction time. After 4 hours, IR (2150 cm) -1 Sample (C) was taken for the purpose of (0.54 g in 2.39 g of tetrachloroethylene): residual Si-H = 307 ppm. An additional Pt catalyst solution (0.063 mL) was added at 4.5 hours. At 6 hours, IR (2150 cm) -1 Sample (D) was taken for (0.54 g in 2.38 g of tetrachloroethylene): residual Si-H = N / D ppm. The reaction was stopped. The substance was removed from the flask after cooling to room temperature. The liquid product (94.13 g) was stored in a plastic bottle. The catalyst used in this reaction was sufficient to provide a total of 20 ppm of Pt. In this reaction, excess allyloxyphenyl-terminated glycol ether was used, and the molar ratio of allyl to Si-H from A-3) and A-4) was approximately 1.3.

[0063] In this Example 11, the SPE copolymer sample SPE-Ph5 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a digital overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated by a heating mantle equipped with a J-KEM temperature controller. In the pot, A-4) DiPPh allyl ether (15.92 g, first portion, about 25%) prepared as described above in Example 4, and B-2) M2D 3.4 D H 3.3 (36.34g) was added. The mixture was heated to 70°C under nitrogen. Pt catalyst solution (0.063mL) was added. This reaction is exothermic, and the temperature rose to 78.5°C. When the temperature dropped to 75°C, the second portion of DiPPh allyl ether (15.97g) was added, and the temperature rose to 69.2°C to 72.4°C. Next, the third portion of DiPPh allyl ether (15.94g) was added along with additional Pt catalyst solution (0.063mL). The temperature rose to 72°C. Next, the final portion of DiPPh allyl ether (15.94g) was added. The J-KEM temperature controller was set to 75°C for the remainder of the reaction time. After 2.5 hours, IR (2150cm²) was used. -1 Sample (A) was taken for the purpose of (0.21 g in 2.15 g of tetrachloroethylene): residual Si-H = 1400 ppm. An additional Pt catalyst solution (0.063 mL) was added over 3 hours. At 4 hours, IR (2150 cm) -1 Sample (B) was taken for (0.37 g in 2.19 g of tetrachloroethylene): residual Si-H = N / D ppm. The reaction was stopped. After the substance cooled to room temperature, it was removed from the flask. The liquid product (97.47 g) was stored in a plastic bottle. The total amount of catalyst used in this reaction was 15 ppm. In this reaction, excess DiPPh allyl ether was used, and the molar ratio of allyl to Si-H was approximately 1.3. The sample was, 1 H, 13 C, and 29 Analysis was performed by Si NMR (using C6D6 as the solvent).

[0064] The copolymers prepared in Examples 7-11 are summarized below in Table 2. The refractive index of the copolymers prepared in Examples 7-11 was measured according to the test method described below and reported in Table 2.

[0065] [Table 3]

[0066] In this Example 12, copolymer sample 12 was synthesized as follows: polyorganohydrogensiloxane (B-3)M2D 38 D H 33 One equivalent (55 g) of D-1) AMS and 5% of the total required D-1) AMS (2.16 g, totaling 43.3 g) were packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the C-1) catalyst, the C-1) catalyst solution described in Table 1 was prepared in IPA (5000 ppm). The temperature was set to 100°C, during which the catalyst solution (enough to provide 10 ppm Pt) was added when the temperature reached 70°C. At T=100°C, 10.28 g of D-1) AMS was added. The second portion of D-1) AMS was added by syringe after 15 minutes (10.28 g), followed by the addition of enough catalyst solution to provide 2 ppm Pt. The third portion of D-1) AMS was added by syringe after 15 minutes (10.28 g), and similarly, enough catalyst solution to provide 2 ppm of Pt was added. The last portion of D-1) AMS was added by syringe after 15 minutes (10.28 g), followed by enough catalyst solution to provide 8 ppm of Pt. After 5 hours and 30 minutes, the temperature was raised to 110°C, and a final addition of catalyst solution to provide 4 ppm of Pt was made. After 1 hour and 30 minutes, the reaction was stopped. The total C-1) catalyst used was sufficient to provide 26 ppm of Pt, and the total time elapsed was 7 hours and 45 minutes.

[0067] In this Example 13, copolymer sample 13 was synthesized as follows: polyorganohydrogensiloxane (B-3)M2D 38 DH 33 A-5) EPh metharyl ether (2 equivalents, 4.27 g) was packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. AMS (31 equivalents) was added in four portions (10.16 g each). The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, C-1) a catalyst solution was prepared in IPA (5000 ppm). The temperature was set to 85°C, during which the catalyst solution (enough to provide 12 ppm Pt) was added when the temperature reached 75°C. At T=85°C, 10.16 g of AMS was added through a dropping funnel and the temperature was increased to 92.3°C. The temperature was lowered back to 85°C over 5 minutes to dropwise add the second portion of AMS (10.16 g). Since no temperature increase was observed, additional catalyst solution (enough to provide 8 ppm of Pt) was added, the temperature was increased by 27°C, and then decreased back to the initial value. This cycle was repeated a total of four times, with additional catalyst solution added in each step (to provide a total of 24 ppm of Pt). After 4 hours and 35 minutes, 1 ¹H-NMR analysis revealed the presence of SiH moieties available for the reaction, but insufficient AMS in the medium. This was likely due to an unexpected leak of AMS from the system. Additional AMS was added to the reactor (7 equivalents, 9.2 g), followed by a sufficient amount of catalyst solution to provide 12 ppm Pt. The temperature was increased to 105°C. The reaction was carried out for a further 3 hours and then completed.

[0068] In this Example 14, copolymer sample 14 was synthesized as follows: SiH source (B-3)M2D 38 D H 33A-6) PPh metharyl ether (1 equivalent, 55 g) and A-6) PPh metharyl ether (2 equivalents, 4.58 g) were packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. D-1) AMS (31 equivalents) was added in four portions (10.16 g each). The contents of the flask were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, C-1) a solution of the catalyst was prepared in IPA (5000 ppm Pt). The temperature was set to 85°C, during which the catalyst solution (enough to provide 12 ppm Pt) was added when the temperature reached 75°C. The remaining reaction was carried out in the same manner as in Example 13 to prepare copolymer sample 13, HT210. The addition of the four AMS portions was completed in 5 hours and 15 minutes with 26 ppm Pt. The conversion was incomplete. The reaction was restarted and heated to 105°C, followed by the addition of excess AMS (26.2 g) and a catalyst solution sufficient to provide 8 ppm of Pt. After 6 hours of reaction, the synthesis was complete, and the excess AMS was removed by stripping.

[0069] In this Example 15, copolymer sample 15 was synthesized as follows: SiH source (B-3)M2D 38 D H 33 1 equivalent (50 g) of A-6)PPh metharyl ether (10% of the total volume, 6.9 g) was packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, a solution of 2-0719 was prepared in IPA (5000 ppm). The temperature was set to 100°C, during which the catalyst solution (enough to provide 24 ppm Pt) was added when the temperature reached 75°C. At T=100°C, 15.5 g of A-6)PPh metharyl ether was added dropwise. The second portion was added after 1 hour, followed by the third portion after another hour. Since no exothermic reaction was observed, enough catalyst solution to provide 6 ppm Pt was added. The temperature was raised to 110°C. 4 mL of toluene was added to aid reflux. After a total of 4 hours and 30 minutes, the final portion of A-6) PPh methallyl ether was added, and the reaction was continued for another 25 minutes before being stopped.

[0070] In this Example 16, copolymer sample 16 was synthesized as follows: SiH source (B-3)M2D 38 D H 33 One equivalent (43.4 g) of A-5) EPh metharyl ether (5.55 g) was packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, a solution of C-1) catalyst was prepared in IPA (5000 ppm). The temperature was set to 85°C, during which the catalyst solution (in an amount sufficient to provide 24 ppm Pt) was added when the temperature reached 75°C. After T=85°C, the first portion of A-5) EPh metharyl ether was added via a dropping funnel (12.5 g). After a reaction time of 5 hours, the third portion of A-5) EPh metharyl ether was added along with enough catalyst solution to provide an additional 4 ppm Pt. The temperature was raised to 100°C and the reaction was allowed to proceed for a further 1.5 hours, after which it was stopped. The reactor was reheated to 100°C. 4 mL of IPA was added along with the last portion of A-5)EPh methallyl ether and an additional amount of catalyst solution sufficient to provide 2 ppm of Pt. After 7 hours, the reaction was stopped. The reaction was still incomplete. The next day, the reactor was reheated to 100°C, and 0.6 g of A-5)EPh methallyl ether was added along with an additional amount of catalyst solution sufficient to provide 4 ppm of Pt, and the reaction was allowed to proceed for another 7 hours. To force completion, the reaction was restarted at 110°C. An additional amount of catalyst solution sufficient to provide 2 ppm of Pt was added, and 9 mL of toluene was added for reflux. A reaction time of 7 hours was completed. Finally, the solvent was stripped to complete the reaction.

[0071] In this Example 17, copolymer sample 17 was synthesized as follows: SiH source (B-3)M2D 38 D H 33A-2) PPh allyl ether (1 equivalent, 55 g) and A-2) PPh allyl ether (2 equivalents, 4.69 g) were packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, a solution of C-1) catalyst was prepared in IPA (5000 ppm). The temperature was set to 85°C, during which the catalyst solution (enough to provide 4 ppm of Pt) was added when the temperature reached 75°C. D-1) AMS (31 equivalents) was added in four portions (10.16 g each). First, two portions of D-1) AMS were added at 85°C, along with enough catalyst solution to provide an additional 2 ppm of Pt at each time point. The third addition did not require any extra catalyst, but after the last portion, enough catalyst solution to provide 2 ppm of Pt was also added. The total reaction time was 5 hours and 40 minutes with 10 ppm Pt. However, the AMS was insufficient, as observed in previous cases. The reactor was heated to 85°C. AMS (30 g) was added dropwise to the reactor, followed by enough catalyst solution to provide 8 ppm Pt. After 7 hours and 30 minutes, the reaction was stopped and the excess AMS was stripped off.

[0072] In this Example 18, copolymer sample 18 was synthesized as follows: SiH source (B-3)M2D 38 D H 331 equivalent (55 g) of EPh allyl ether (A-1) and 2 equivalents (4.35 g) were packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, a solution of 2-0719 was prepared in IPA (5000 ppm). The temperature was set to 85°C, during which the catalyst solution (enough to provide 4 ppm of Pt) was added when the temperature reached 75°C. 31 equivalents of D-1) AMS (10.16 g each) were added in four portions as follows: At 85°C, the first portion was added, followed by an additional amount of catalyst solution sufficient to provide 4 ppm of Pt. Adding this raised the temperature to 120°C. After stabilizing the temperature at 85°C, the remaining three portions of D-1) AMS were added in succession, and the reaction was allowed to proceed for 1.5 hours after each addition. The reaction was completed in 7 hours.

[0073] In this Example 19, copolymer sample 19, HT174, was synthesized as follows: SiH source (B-3) M2D 38 D H 33 1 equivalent (50 g) of A-2)PhPO1 (7 g, 10% of the total volume) was packed into a 250 mL three-necked round-bottom flask equipped with a condenser, magnetic rod, and N2 inlet. The contents were stirred at room temperature until a homogeneous mixture was obtained. To insert the catalyst, a solution of 2-0719 was prepared in IPA (5000 ppm). The temperature was set to 85°C, during which the catalyst solution (enough to provide 4 ppm Pt) was added when the temperature reached 75°C. At T=85°C, the first portion of A-2)PPh allyl ether (15.8 g) was added dropwise. The same procedure was repeated a total of four times. The reaction was completed after approximately 7 hours.

[0074] In this Example 20, the SPE copolymer sample 20 (SPE-Ph-EO1) was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a digital overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a J-KEM temperature controller. In the pot, A-1) EPh allyl ether (7 g, first part, 10%) and M2D 38 D H 33 (45g) was added. The mixture was heated to 70°C under nitrogen. Catalyst C-1) was added (enough to provide 4 ppm of Pt). This reaction was exothermic, and the temperature rose to 98°C. The temperature was then reduced to 73°C over 1 hour. The second portion (15g) of A-1) EPh allyl ether was added dropwise through a funnel. The temperature rose to 89°C and decreased to 73°C over 45 minutes. Another 15g of A-1) EPh allyl ether was added, and the temperature was increased to 83°C over several minutes. Catalyst C-1) was added in an amount sufficient to provide 4 ppm of Pt, the temperature was raised to 90°C, and 3 mL of isopropanol was added to induce the reaction. After 1 hour, the last portion of 15g of EPh allyl ether was added along with an additional amount of C-1) catalyst to provide 4 ppm of Pt, and the reaction was allowed to continue for another hour before being stopped.

[0075] In this Example 21, the sample SPE copolymer sample 21 (SPE-AMS-mPh-PO1) was prepared as follows: First, a mixture of D-1) AMS and A-6) PPh methallyl ether (monomer blend) was prepared using equal amounts of each. The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a digital overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated by a heating mantle equipped with a J-KEM temperature controller. In the pot, the monomer blend (6 g, first part, 10%) and M2D 38 D H 33(55g) was added. The mixture was stirred under nitrogen for 5 minutes, and then the temperature was set to 100°C. When the temperature reached 70°C, enough catalyst C-1) to provide 12 ppm of Pt was added. The remainder of the monomer blend was added dropwise in four different portions (14.85g each), and the exothermic trend was monitored with an IR probe. After each addition, enough catalyst C-1) to provide 3–6 ppm of Pt was added, which caused an increase in temperature. The next monomer blend was added after waiting for the temperature to drop to 100°C and stabilize. The reaction was carried out in total for 5 hours and then stopped. On the second day, the flask was reheated to 100°C and the reaction was carried out for a further 3 hours, with enough catalyst C-1) to provide 3 ppm of Pt (45 ppm of Pt in total) to bring the reaction to completion. Excess monomer remained in the mixture.

[0076] In this Example 22, the SPE copolymer sample 22 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a mechanical overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a PT-100 temperature controller. In a flask at room temperature, A-6) PPh metharyl ether (1.25 g, first part, 5%) and 30.01 g of M2D 52.5 D H 21.1A and a blend were created. The mixture was heated to 75°C under nitrogen. After 25 minutes, when the temperature reached 76°C, ±6 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. This reaction is exothermic, and the temperature rose to 80°C in 27 minutes. The temperature was set to 100°C. At 53 minutes, when the temperature reached 99.3°C, the second portion (5.54 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 5 minutes. At 1 hour and 2 minutes, when the temperature was 101.7°C, the second dose (5000 ppm activity level) of Pt catalyst in IPA was added (0.070 g / ±5 ppm). The temperature reached 108°C in 1 hour and 4 minutes. At 2 hours and 42 minutes, when the temperature reached 102.4°C, the third portion (6.17 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 4 minutes. At 2 hours and 55 minutes, when the temperature was 103°C, the third dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.064 g / ±5 ppm). The temperature reached 104.3°C at 2 hours and 56 minutes. At 3 hours and 52 minutes, when the temperature reached 100.4°C, the fourth portion (5.87 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 1 minute. At 4 hours and 5 minutes, when the temperature was 102.2°C, the fourth dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.05 g / ±4 ppm). The temperature reached 103.6°C at 4 hours and 6 minutes. At 4 hours and 37 minutes, when the temperature reached 103.1°C, the final portion (5.89 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 1 minute. The reaction was stopped after 6 hours and 38 minutes at a temperature of 99.6°C, and H+ NMR was performed to confirm whether unreacted SiH was still present. Two days after restarting the reaction, and again after 1 hour and 14 minutes when the temperature reached 99.2°C, ±3 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. The reaction was stopped after 3 hours and 57 minutes when the temperature was 98.1°C, and another H+ NMR was performed. This second NMR analysis confirmed that no more reacting SiH was present. A total of 27.55 ppm of catalyst was used.

[0077] In this Example 23, the SPE copolymer sample 23 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a mechanical overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a PT-100 temperature controller. In a flask at room temperature, A-6) PPh metharyl ether (1.25 g, first part, 4%) and 25 g of M2D 23.1 D H 20A and a blend were created. The mixture was heated under nitrogen. After 16 minutes, when the temperature reached 100.8°C, ±6 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. This reaction is exothermic, and the temperature rose to 107.7°C in 17 minutes. At 43 minutes, when the temperature reached 97.3°C, the second portion (5.6 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 8 minutes - the temperature reached 110.2°C. At 53 minutes, when the temperature was 110.1°C, the second dose (5000 ppm activity level) of Pt catalyst in IPA was added (0.059 g / ±6 ppm). The temperature reached 112.7°C in 54 minutes. At 2 hours and 27 minutes, when the temperature reached 105.4°C, the third portion (6.22 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 4 minutes. At 2 hours and 47 minutes, when the temperature reached 102°C, the fourth portion (6.54 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 6 minutes. At 3 hours and 33 minutes, when the temperature reached 102.4°C, the fifth portion (7 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 1 minute. At 4 hours and 18 minutes, when the temperature reached 102.4°C, the last portion (6.84 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 5 minutes. At 4 hours and 56 minutes, when the temperature was 102.2°C, the third dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.03 g / ±3 ppm). At 5 hours and 37 minutes, when the temperature was 100.7°C, the reaction was stopped, and H+ NMR was performed to confirm whether unreacted SiH was still present. The following day (August 26, 2022), the reaction was restarted, and ±3 ppm of Pt catalyst (5000 ppm activity level) in IPA was added at 3 hours and 29 minutes when the temperature reached 103.2°C. At 5 hours and 45 minutes, when the temperature was 105°C, the remaining dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.026 g / ±3 ppm). At 6 hours and 40 minutes, when the temperature was 103.6°C, the remaining dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.021 g / ±3 ppm). At 7 hours and 13 minutes, when the temperature was 103.4°C, the reaction was stopped, and another H+ NMR was performed. This second NMR analysis confirmed that no more SiH molecules were present to react. A total of 21.49 ppm of catalyst was used.

[0078] In this Example 24, the SPE copolymer sample 24 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a mechanical overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a PT-100 temperature controller. In a flask at room temperature, A-6) PPh metharyl ether (2.5 g, first portion, 6.5%) and 17.51 ​​g of M2D 21.4 D H 50A blend was formed. The mixture was heated to 100°C under nitrogen. After 18 minutes, when the temperature reached 100.5°C, ±6 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. This reaction was exothermic, and the temperature rose to 115.2°C in 19 minutes. At 35 minutes, when the temperature reached 100.4°C, the second portion (5.6 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 5 minutes. At 41 minutes, when the temperature was 100°C, the second dose (5000 ppm activity level) of Pt catalyst in IPA was added (0.035 g / ±3 ppm). The temperature reached 102.5°C in 42 minutes. At 60 minutes, when the temperature reached 100.2°C, the third portion (10.06 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 3 minutes. At 2 hours and 27 minutes, when the temperature reached 101.2°C, the fourth portion (6.03 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 4 minutes. At 3 hours and 13 minutes, when the temperature reached 100.8°C, the fifth portion (5.61 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 2 minutes. At 4 hours and 0 minutes, when the temperature reached 99.5°C, the last portion (8.47 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 2 minutes. At 4 hours and 22 minutes, when the temperature was 100°C, the third dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.065 g / ±6 ppm). At 5 hours and 45 minutes, when the temperature was 100.2°C, the reaction was stopped, and H+ NMR was performed to confirm whether unreacted SiH was still present. The following day (September 15, 2022), the reaction was restarted, and at 54 minutes when the temperature reached 100°C, ±6 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. At 1 hour and 40 minutes when the temperature was 99°C, the dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.032 g / ±3 ppm). At 4 hours and 12 minutes when the temperature was 100.5°C, the dose of IPA (0.842 g) was added to increase the compatibility between methallyl and SiH. At 5 hours and 14 minutes when the temperature was 102.5°C, the dose of Pt catalyst in IPA (5000 ppm activity level) was added (0.055 g / ±5 ppm) - the temperature increased to 103.6°C at 5 hours and 16 minutes. At 6 hours and 20 minutes when the temperature was 100°C, the reaction was stopped and another H+ NMR was performed.This second NMR analysis confirmed that no more SiH molecules were present to react. A total of 27.46 ppm of catalyst was used.

[0079] In this Example 25, the SPE copolymer sample 25 was prepared as follows: The hydrosilylation reaction was carried out in a 250 mL four-necked round-bottom flask equipped with a mechanical overhead stirrer, thermocouple, stopper, condenser, and nitrogen inlet. This system was heated with a heating mantle equipped with a PT-100 temperature controller. In a flask at room temperature, A-6) PPh metharyl ether (4.48 g, first portion, 13.5%) and 25.65 g of M2D 57.5 D H 44A blend was formed. The mixture was heated to 100°C under nitrogen. After 31 minutes, when the temperature reached 97°C, ±5 ppm of Pt catalyst (5000 ppm activity level) in IPA was added. No exothermic reaction was observed in this example. At 44 minutes, when the temperature was 99.5°C, 0.34 g of IPA was added to increase the compatibility between methallyl and SiH. With the temperature controller set to 102°C, exothermic reaction was observed at 52 minutes (105.3°C). At 1 hour and 3 minutes, when the temperature reached 98.6°C, a second portion (5.99 g) of A-6) PPh methallyl ether was added dropwise through a funnel over 2 minutes. At 1 hour and 29 minutes, when the temperature was 100°C, a second dose of Pt catalyst (5000 ppm activity level) in IPA was added (0.072 g / ±5 ppm). At 1 hour and 35 minutes, when the temperature reached 100.6°C, the third portion (11.08 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 3 minutes. At 3 hours and 42 minutes, when the temperature was 101°C, the third dose of the Pt catalyst in the IPA (5000 ppm activity level) was added (0.071 g / ±5 ppm). At 3 hours and 46 minutes, when the temperature reached 101.2°C, the final portion (11.54 g) of A-6) PPh metharyl ether was added dropwise through a funnel over 6 minutes. At 4 hours and 27 minutes, when the temperature was 101.5°C, the fourth dose of the Pt catalyst in the IPA (5000 ppm activity level) was added (0.159 g / ±13 ppm) - the temperature reached 102.4°C at 4 hours and 29 minutes. The reaction was stopped after 6 hours and 19 minutes at a temperature of 99.7°C, and H+ NMR was performed to confirm whether any unreacted SiH remained. This NMR analysis confirmed that no more reacting SiH was present. A total of 24.51 ppm of catalyst was used.

[0080] In this Example 26, SPE copolymer sample 26 was prepared by repeating the procedure in Example 22.

[0081] [Table 4]

[0082] In this foam control example A, the SPE copolymer and comparative copolymer prepared as described above were evaluated for their foam control performance using a Quick Suds Test for Antifoam Performance, either with or without silicone resin and silica (neat). The Quick Suds Test for Antifoam Performance was performed by adding 300 mL of water with a specified water hardness (23° French hardness) to a rotating tube, as described below. Either the neat copolymer or 0.7 g of a detergent formulation from Table D containing a copolymer as a candidate for the antifoaming agent was added. The tube was rotated at 30 RPM for 9 minutes. Next, the foam height (cm) was measured. Without the candidate antifoaming agent, the tube was filled with foam at the end of the 9 minutes of rotation (24 cm). The amount of copolymer added was either 0.1% or 0.5%, and the results of the Quick Suds Test are shown below in Tables 4 and 5.

[0083] [Table 5]

[0084] [Table 6]

[0085] The data in Table 4 shows that all SPE copolymers tested neat exhibited better foam control properties than the control (the copolymer of Example 12, which has pendant groups derived from alpha-methylstyrene but not from alkenyloxyphenyl-terminated glycol ethers). The SPE copolymers of the present invention offer the unexpected advantage of providing good foam control properties in the absence of MQ resin and silica, which makes these SPE copolymers suitable for simpler foam control formulations than foam control formulations currently on the market that contain silicone resins and hydrophobic fillers. Surprisingly, SPE copolymers having silicon-bonded pendant groups derived from allyloxyphenyl-terminated glycol ethers but not pendant groups derived from alpha-methylstyrene (i.e., the SPE copolymers of Examples 15, 16, 19, and 20) exhibited better foam control characteristics, particularly at a 0.5% input, than SPE copolymers containing pendant groups derived from both alpha-methylstyrene and allyloxyphenyl-terminated glycol ethers (i.e., the SPE copolymers of Examples 13, 14, and 21) under the conditions tested in this example.

[0086] In this foam-controlled formulation example I (FCF I), the foam-controlled formulation sample was prepared as follows: 8.7 g of the SPE copolymer (or comparative copolymer) synthesized as described above, 0.7 g of MQ resin, and 0.6 g of Sipernat D10-1 were weighed into a 20 mL plastic container suitable for a Hauschild Speed ​​mixer. The resulting blend was mixed for 30 seconds at 3500 RPM for the first time. The plastic container was opened and inspected to check for the possibility of silica aggregates. If necessary to break up silica aggregates, a second mix of 30 seconds at 3500 RPM was applied. A specific foam-controlled formulation prepared as described in this example was evaluated using the rapid foam test described below. The results are shown below in Table 5.

[0087] [Table 7]

[0088] The data in Table 5 shows that all SPE copolymers tested provided good foam control in conventional foam-controlling formulations containing silicone resin and silica filler under the tested conditions. Certain SPE copolymers showed improved foam control performance compared to the comparative examples. The SPE copolymers of Examples 21-26 showed improved foam control performance (compared to the comparative copolymers) under the conditions tested in these examples, even though these SPE copolymers did not contain any pendant groups derived from alpha-methylstyrene.

[0089] In this foam control formulation example II, the foam control formulation prepared in foam control formulation example I was evaluated using the washing machine defoaming procedure described below. The results are shown in Tables 6, 7, and 8 below.

[0090] [Table 8]

[0091] The data in Table 6 shows that SPE copolymers having silicon-bonded pendant groups derived from both alpha-methylstyrene and alkenyloxyphenyl-terminated glycol ethers provided good defoaming performance in the tested foam-controlling formulations. Using the SPE copolymer of Example 14, sample FCF I-14, which contained a silicon-bonded pendant group derived from A-6)PPh methallyl ether, showed improved foam-controlling performance compared to the control, which had a silicon-bonded pendant group derived from alpha-methylstyrene but lacked the alkenyloxyphenyl-terminated glycol ether.

[0092] [Table 9]

[0093] The data in Table 7 shows that SPE copolymers having silicon-bonded pendant groups derived from alkenyloxyphenyl-terminated glycol ethers (none derived from alpha-methylstyrene) provided some foam control performance under the conditions tested in this example, although not as well as SPE copolymers containing silicon-bonded pendant groups derived from both alpha-methylstyrene and alkenyloxyphenyl-terminated glycol ethers (shown above in Table 6).

[0094] [Table 10]

[0095] The data in Table 8 shows that a foam-controlling formulation containing an SPE copolymer having 2 equivalents of pendant groups derived from alkenyloxyphenyl-terminated glycol ethers and 31 equivalents of pendant groups derived from alpha-methylstyrene provided the best defoaming performance under the tested conditions. The foam-controlling performance of this sample FCF I-14 was better than that of the comparative example (where the copolymer had pendant groups derived from alpha-methylstyrene but not from alkenyloxyphenyl-terminated glycol ethers). Other samples tested showed some foam-controlling performance.

[0096] In this foam-controlled formulation Example III, the SPE copolymer prepared in Example 15 was incorporated into a foam-controlled formulation containing a different silicone resin. The sample was prepared as described in foam-controlled formulation Example I, except for the use of the SPE copolymer from Example 15 and the silicone resins listed below in Table 9.

[0097] [Table 11]

[0098] The following washing machine defoaming procedure was completed for the samples in Table 9. Good defoaming performance was obtained using all the MQ resins tested. MQ resin (III) was found to provide better defoaming performance than MQ resin (IV) when all other starting materials were the same as those tested in this example. No significant difference was observed between MQ resin (I) and MQ resin (II) under the tested conditions.

[0099] In this foam-controlling formulation Example IV, the SPE copolymers from Examples 15 and 22-25 were incorporated into the foam-controlling formulation using the procedure of foam-controlling formulation Example I, except that the selected SPE copolymer was changed. The foam-controlling formulation was evaluated using the washing machine defoaming procedure described below. The results are shown in Table 10.

[0100] [Table 12]

[0101] The examples in Table 10 demonstrate that the use of an SPE copolymer derived from alpha-methylstyrene that lacked silicon-bonded pendant groups provided some foam control performance under the conditions tested in these examples.

[0102] It is well known in the personal care industry that phenyl-functional silicone polymers provide a glossy effect to hair. Gloss is desirable for the appearance of healthy hair. Gloss varies depending on hair type, hair damage, hair alignment, and the refractive index (refractive index, RI) of the substance deposited on the hair. Existing phenyl-functional silicones used as a control, which provide high gloss, such as DOWSIL® 556 Cosmetic Fluid (phenyl trimethicone), can be expensive and difficult to manufacture. Therefore, SPE copolymers with high RI values ​​may be attractive as alternatives in hair care formulations. The refractive indices of certain alkenyloxyaryl-terminated glycol ethers, SPE copolymers, and control materials were evaluated as described in the test methods below and reported in Table 12.

[0103] [Table 13]

[0104] The data in Table 12 suggest that SPE copolymers prepared as described herein may be useful in hair care compositions. SPE copolymers may also offer the additional advantage of lower manufacturing costs than current phenyl-functionalized siloxanes such as DOWSIL® 556 Fluid.

[0105] The SPE copolymer material (0.0453 g) from Example 7 and decamethylcyclopentasiloxane (0.19642 g, XIAMETER® PMX-0245, manufactured by Dow) were combined by mixing. The resulting mixture was used to treat hair bundles (dark bleached hair bundles from International Hair Importers, washed with this treatment). The bundles showed an average increase of 12% in shine.

[0106] Rapid foam test for defoaming performance 300 mL of water with the specified water hardness (23° French hardness) was added to a rotating tube. 0.7 g of a detergent formulation from Table D containing a copolymer was added as a candidate for the defoaming agent. The tube was rotated at 30 RPM for 9 minutes. Next, the foam height (cm) was measured. Without the candidate defoaming agent, the tube was filled with foam (24 cm) at the end of the 9 minutes of rotation.

[0107] [Table 14]

[0108] Washing machine defoaming procedure: In a Miele W1914 container containing either 11 clean terry towels (2 kg dry weight) or 16 clean terry towels (3.5 kg), 50 g of the detergent formulations listed above in Table D, containing 0.1% by weight of defoamer, was added along with 15 liters of soft water unless otherwise specified. The hardness was manually adjusted for washing by adding 5 mL of calcium ion solution (262 g CaCl2·2H2O / liter) and 19 mL of magnesium ion solution (72 g MgCl2 / liter). The 40°C cotton program was used at a rotation speed of 1400 rpm, and the foam height in the front window was monitored every 5 minutes throughout the entire wash cycle. After this test, two additional wash cycles (with temperatures set to 95°C and then 40°C) were followed to remove any defoamer residue and avoid detergent buildup.

[0109] Refractive index The refractive index (RI) was measured as follows: The refractive index of the synthesized material was measured using a BAUSCH & LOMB refractometer, model #CSA B 2550. The sample was placed between two prisms that had been cleaned with IPA and dried using tissue paper. The refractive index measurement was performed after color correction, observing that the boundary of the sample turned blue on one side and slightly red on the other. [Industrial applicability]

[0110] The above examples demonstrate that alkenyloxyphenyl-terminated glycol ethers and silicone-polyether copolymers prepared using them can be successfully synthesized as described herein, and that both the tested alkenyloxyphenyl-terminated glycol ethers and silicone-polyether copolymers had high refractive indices (e.g., RI > 1.460). Silicone-polyether copolymers may be used in a variety of applications, such as hair care compositions, other personal care compositions, pressure-sensitive adhesive compositions, and coating compositions, such as release coating compositions. Alternatively, silicone-polyether copolymers may be useful as wetting agents, thickeners, or surfactants, such as surfactants in urethane foams as disclosed in U.S. Patent No. 5,869,727, in addition to or instead of the silicone-polyether copolymers described therein.

[0111] The above examples also demonstrate that the silicone-polyether copolymers described herein are useful as foam control agents. The copolymers may be used as is (for example, without silicone resin and / or hydrophobic fillers in the foam control formulation) and provide good foam control, as shown in foam control example A. Certain SPE copolymers (e.g., SPE copolymers having silicon-bonded pendant groups derived from allyloxy, phenyl-terminated glycol ethers but not pendant groups derived from alpha-methylstyrene) may, when used as is, provide better foam control than SPE copolymers having both silicon-bonded pendant groups derived from allyloxy, phenyl-terminated glycol ethers and silicon-bonded pendant groups derived from alpha-methylstyrene, as shown in Table 4. Other SPE copolymers, for example, SPE copolymers having both silicon-bonded pendant groups derived from allyloxy, phenyl-terminated glycol ethers and silicon-bonded pendant groups derived from alpha-methylstyrene, may provide better foam control properties when incorporated into foam control compositions containing fillers (e.g., silica) and silicone resins (e.g., MQ resins), as shown in Tables 5 and 7. While not bound by theory, it is conceivable that the SPE copolymer of the present invention can be prepared using selected starting materials to provide an SPE copolymer that offers good foam control for a variety of different applications, such as foam control formulations and / or detergent compositions.

[0112] Definitions and Use of Terms All quantities, ratios, and percentages herein are by weight unless otherwise indicated by the context of the specification. The articles “a,” “an,” and “the” each refer to one or more unless otherwise indicated by the context of the specification. The singular form includes the plural form unless otherwise indicated by the context of the specification. The “Summary of the Invention” and “Abstract” are incorporated herein by reference. The total amount of all starting materials in a composition is 100%. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in Sections §2111.03 I, II, and III of the “Manual of Patent Examining Procedure Ninth Edition,” Revision 08.2017, Last Revised January 2018. Any feature or aspect of the present invention may be used in combination with any other feature or aspect listed herein. Abbreviations used herein have their definitions in Table 13.

[0113] [Table 15]

Claims

1. A silicone polyether copolymer comprising the following unit formula, (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ R ２ SiO ２／２ ) ｃ (R １ ２ R ２ SiO １／２ ) ｄ (R １ SiO ３／２ ) ｅ (R ２ SiO[[ID=Id=40]] ３／２ ) ｆ (SiO ４／２ ) ｇ , wherein The subscripts a, b, c, d, e, f, and g represent the average number of each unit in the unit formula. a ≥ 0, d≧0, Amount (a+d)≧2, b ≥ 0, c ≥ 1, e≧0, f≧0, quantity (c+d+f)≧1, g≧0, The quantity (a + b + c + d + e + f + g) has a value between 2 and 10,000. Each R １ However, it is an alkyl group consisting of 1 to 12 independently selected carbon atoms. Each R ２ However, independently selected from the group consisting of H, formula E1'), formula D1'), and formula A1'), Equation E1') is, 【Chemistry 1】 And in the formula, R １ However, as stated above, the subscript m is 0 or 1, and each R ６ However, it is a divalent hydrocarbon group, Equation D1') is, 【Chemistry 2】 And in the formula, Each R is independently selected from the group consisting of H, halogen atoms, OH, methyl, and methoxy. D' is a covalent bond, the formula -CH ２ -Base, or formula -CH ２ It is the base of -O-, R is either H or methyl. Equation A1') is, 【Transformation 3】 And in the formula, X is H or methyl, D is the experimental formula - C ２ H ４ - or -C ３ H ６ - has, Each R ３ However, independently selected from H, halogen atoms, OH, methyl, and methoxy, The subscript n is 1, 2, or 3. However, at least one R per molecule ２ A silicone polyether copolymer having formula A1'.

2. Each R ２ The copolymer according to claim 1, wherein the copolymer is selected from formula D1') and formula A1').

3. Equation D1') is, 【Chemistry 4】 The copolymer according to claim 1 or 2.

4. i) D is -CH ２ -CH ２ - or - CH ２ -CH(CH ３ ) - Selected from the group consisting of, ii) The subscript n is 1 or 2, or The copolymer according to any one of claims 1 to 3, wherein both iii)i) and ii).

5. The copolymer is linear and has a unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ R ２ SiO ２／２ ) ｃ (R １ ２ R ２ SiO １／２ ) ｄ Including, in the formula, a = 0, 1, or 2 d = 0, 1, or 2 Amount (a+d)=2, b = 3 to 100, c = 3 to 100, The copolymer according to any one of claims 1 to 4, wherein the quantity (b + c) = 6 to 150.

6. d = 0, and the copolymer has the unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ R ２ SiO ２／２ ) ｃ Including, in the formula, a = 2, b = 3.4 to 57, c = 3.3 to 50, The copolymer according to claim 5, wherein the amount (b + c) = 6.7 to 101.

7. A method for producing a copolymer according to any one of claims 1 to 6, wherein the method is 1) Under the conditions necessary for carrying out the hydrosilylation reaction, A) Formula 【Transformation 5】 an alkenyloxyaryl-terminated glycol ether, wherein, X is H or methyl, D is the experimental formula - C ２ H ４ - or -C ３ H ６ - has, Each R ３ However, independently selected from H, halogen atoms, OH, methyl, and methoxy, Alkenyloxyaryl-terminated glycol ethers in which the subscript n is 1, 2, or 3, B) Unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ HSiO ２／２ ) ｃ (R １ ２ HSiO １／２ ) ｄ (R １ SiO ３／２ ) ｅ (HSiO ３／２ ) ｆ (SiO ４／２ ) ｇ is a polyorganohydrogensiloxane containing, wherein, The subscripts a, b, c, d, e, f, and g represent the average number of each unit in the above formula. a ≥ 0, d≧0, Amount (a+d)≧2, b ≥ 0, c ≥ 1, e≧0, f≧0, quantity (c+d+f)≧1, g≧0, The quantity (a + b + c + e + f + g) has a value between 2 and 10,000. Each R １ However, polyorganohydrogensiloxanes, which are alkyl groups with 1 to 12 carbon atoms, C) A method comprising combining a hydrosilylation reaction catalyst with a starting material containing the catalyst.

8. The aforementioned starting material is D) Formula D1) 【Transformation 6】 It further contains the aromatic compound, in which, Each R is independently selected from the group consisting of H, halogen atoms, OH, methyl, and methoxy. D' is a covalent bond, the formula -CH ２ -Base, or formula -CH ２ It is the base of -O-, The method according to claim 7, wherein R'' is H or methyl.

9. The method according to claim 8, wherein D) is selected from the group consisting of styrene, α-methylstyrene, eugenol, allylbenzene, allylphenyl ether, 2-allylphenol, 2-chlorostyrene, 4-chlorostyrene, 4-methylstyrene, 3-methylstyrene, 4-t-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, and 2,4,6-trimethylstyrene.

10. The aforementioned starting material is E) formula 【Transformation 7】 The formula further comprises a dialkenyl-terminated siloxane oligomer, where R １ However, as stated above, each R ５ The method according to any one of claims 7 to 9, wherein the alkenyl group is independently selected from 2 to 6 carbon atoms, and the subscript m is 0 or 1.

11. A) The alkenyloxyphenyl-terminated glycol ether is A-1) Formula C ６ H ５ -O-CH ２ -CH ２ -O-CH ２ -CH=CH ２ (2-(allyloxy)ethoxy)benzene, A-2) Formula C ６ H ５ -O-CH ２ -CH(CH ３ )-O-CH ２ -CH=CH ２ (2-(allyloxy)propoxy)benzene, A-3) Formula C ６ H ５ -O-CH ２ -CH ２ -O-CH ２ -CH ２ -O-CH ２ -CH=CH ２ (2-(2-(allyloxy)ethoxy)ethoxybenzene, A-4) Formula C ６ H ５ -O-CH ２ -CH(CH ３ )-O-CH ２ -CH(CH ３ )-O-CH ２ -CH=CH ２ (2-(2-(allyloxy)propoxy)propoxy)benzene, A-5) Formula C ６ H ５ -O-CH ２ -CH ２ -O-CH ２ -C(CH ３ ) = CH ２ (2-((2-methylallyl)oxy)ethoxy)benzene, and A-6) Formula C ６ H ５ -O-CH ２ -CH(CH ３ )-O-CH ２ -C(CH ３ ) = CH ２ The method according to any one of claims 7 to 10, selected from the group consisting of (2-((2-methylallyl)oxy)propoxy)benzene.

12. B) The polyorganohydrogensiloxane is linear and has a unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ HSiO ２／２ ) ｃ (R １ ２ HSiO ２／２ ) ｄ Including, in the formula, R １ However, as stated above, a = 0, 1, or 2 d = 0, 1, or 2 Amount (a+d)=2, b = 3 to 100, c = 3 to 100, The method according to any one of claims 7 to 11, wherein the quantity (b + c) = 6 to 150.

13. d = 0, and B) the polyorganohydrogensiloxane has a unit formula (R １ ３ SiO １／２ ) ａ (R １ ２ SiO ２／２ ) ｂ (R １ HSiO ２／２ ) ｃ Including, in the formula, R １ However, as stated above, a = 2, b = 3.4 to 57, c = 3.3 to 50, The method according to claim 12, wherein the quantity (b + c) = 6.7 to 101.

14. The alkenyloxyphenyl-terminated glycol ether of the following formula, 【Transformation 8】 During the ceremony, X is H or methyl, D is the experimental formula - C ２ H ４ - or -C ３ H ６ - has, The subscript n is 1, 2, or 3. However, X = H and D = -C ２ H ４ - When this is true, an alkenyloxyphenyl-terminated glycol ether, provided that the subscript n is 2 or 3.

15. The aforementioned alkenyloxyphenyl-terminated glycol ether (2-(allyloxy)propoxy)benzene, (2-(2-(allyloxy)ethoxy)ethoxy)benzene, (2-(2-(allyloxy)propoxy)propoxy)benzene, (2-((2-methylallyl)oxy)ethoxy)benzene, (2-((2-methylallyl)oxy)propoxy)benzene, (2-(2-((2-methylallyl)oxy)ethoxy)ethoxy)benzene, and The alkenyloxyphenyl-terminated glycol ether according to claim 14, selected from the group consisting of (2-(2-((2-methylallyl)oxy)propoxy)propoxy)benzene.

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