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EP-4739732-A1 - SILICONE - POLYETHER COPOLYMER AND METHOD FOR SYNTHESIS THEREOF

EP4739732A1EP 4739732 A1EP4739732 A1EP 4739732A1EP-4739732-A1

Abstract

A silicone - polyether copolymer and methods for its preparation and use are disclosed. The silicone - polyether copolymer is useful in various applications including hair care compositions due to having a refractive index > 1.46.

Inventors

  • BALIJEPALLI, SUDHAKAR
  • JOFFRE, ERIC

Assignees

  • Dow Silicones Corporation

Dates

Publication Date
20260513
Application Date
20240619

Claims (15)

  1. CLAIMS: 1. A silicone - polyether copolymer comprising unit formula: (R 1 3SiO1/2)a(R 1 2SiO2/2)b(R 1 R 2 SiO2/2)c(R 1 2R 2 SiO1/2)d(R 1 SiO3/2)e(R 2 SiO3/2)f(SiO4/2)g, where subscripts a, b, c, d, e, f, and g represent average numbers of each unit in the unit formula and have values such that a ≥ 0; d ≥ 0; a quantity (a + d) ≥ 2; b ≥ 0; c ≥ 1; e ≥ 0; f ≥ 0; a quantity (c + d + f) ≥ 1; g ≥ 0; a quantity (a + b + c + d + e + f + g) = 2 to 10,000; each R 1 is an independently selected alkyl group of 1 to 12 carbon atoms; and each R 2 is independently selected from the group consisting of H, formula E1’), formula D1’), and formula A1’), where as described formul re he 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 - CH 2 -O-; and R” is H or methyl; and D has empirical formula -C 2 H 4 - or -C 3 H 6 -, each R 3 is independently selected from H, a halogen atom, OH, methyl, and methoxy; and subscript n is 1, 2, or 3; and with the proviso that at least one R 2 per molecule has formula A1’).
  2. 2. The copolymer of claim 1, where each R 2 is selected from formula D1’) and formula A1’).
  3. 3. The copolymer of claim 1 or claim 2, where formul .
  4. 4. The copolymer of any one of claims 1 to 3, where i) D is selected from the group consisting of -CH2-CH2- or -CH2-CH(CH3)-, or ii) subscript n is 1 or 2, or iii) both i) and ii).
  5. 5. The copolymer of any one of claims 1 to 4, where the copolymer is linear and comprises 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 , where a = 0, 1, or 2; d = 0, 1, or 2; a quantity (a + d) = 2; b = 3 to 100; c = 3 to 100; and a quantity (b + c) = 6 to 150.
  6. 6. The copolymer of claim 5, where d = 0, and the copolymer comprises unit formula (R 1 3SiO1/2)a(R 1 2SiO2/2)b(R 1 R 2 SiO2/2)c, where a = 2; b = 3.4 to 57; c = 3.3 to 50; and a quantity (b + c) = 6.7 to 101.
  7. 7. A method for making the copolymer of any one of claims 1 to 6, wherein the method comprises: 1) combining, under conditions to effect hydrosilylation reaction, starting materials comprising A) an alkenyloxy-, aryl- terminated glycol ether of formula re D has empirical formula -C2H4- or -C3H6-, each R 3 is independently selected from H, a halogen atom, OH, methyl, and methoxy, and subscript n is 1, 2, or 3; B) a polyorganohydrogensiloxane comprising 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 , where subscripts a, b, c, d, e, f, and g represent average numbers of each unit in the formula and have values such that a ≥ 0; d ≥ 0; a quantity (a + d) ≥ 2; b ≥ 0; c ≥ 1; e ≥ 0; f ≥ 0; a quantity (c + d + f) ≥ 1; g ≥ 0; a quantity (a + b + c + e + f + g) = 2 to 10,000; each R 1 is an alkyl group of 1 to 12 carbon atoms; and C) a hydrosilylation reaction catalyst.
  8. 8. The method of claim 7, where the starting materials further comprise: D) an aromatic compound of formula re each R is inde nsisting 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.
  9. 9. The method of claim 8, where D) is selected from the group consisting of styrene, α-methyl styrene, eugenol, allylbenzene, allyl phenyl 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. 10. The method of any one of claims 7 to 9, where the starting materials further comprise E) dialkenyl-terminated siloxane oligomer of R 1 is as described above, each R 5 is an atoms, and subscript m is 0 or 1.
  11. 11. The method of any one of claims 7 to 10, where A) the alkenyloxy-, phenyl- terminated glycol ether is selected from the group consisting of: A-1) (2-(allyloxy)ethoxy)benzene of formula C6H5-O-CH2-CH2-O-CH2-CH=CH2, A-2) (2-(allyloxy)propoxy)benzene of formula C 6 H 5 -O-CH 2 -CH(CH 3 )-O-CH 2 -CH=CH 2 , A-3) (2-(2-(allyloxy)ethoxy)ethoxy)benzene of formula C6H5-O-CH2-CH2-O-CH2-CH2- O-CH 2 -CH=CH 2 , A-4) (2-(2-(allyloxy)propoxy)propoxy)benzene of formula C 6 H 5 -O-CH 2 -CH(CH 3 )-O- CH 2 -CH(CH 3 )-O-CH 2 -CH=CH 2 , A-5) (2-((2-methylallyl)oxy)ethoxy)benzene of formula C6H5-O-CH2-CH2-O-CH2- C(CH 3 )=CH 2 , and A-6) (2-((2-methylallyl)oxy)propoxy)benzene of formula C6H5-O-CH2-CH(CH3)-O- CH 2 -C(CH 3 )=CH 2 .
  12. 12. The method of any one of claims 7 to 11, where B) the polyorganohydrogensiloxane is linear and comprises unit formula (R 1 3SiO1/2)a(R 1 2SiO2/2)b(R 1 HSiO2/2)c(R 1 2HSiO2/2)d, where R 1 is as described above; a = 0, 1, or 2; d = 0, 1, or 2; a quantity (a + d) = 2; b = 3 to 100; c = 3 to 100; and a quantity (b + c) = 6 to 150.
  13. 13. The method of claim 12, where d = 0, and B) the polyorganohydrogensiloxane comprises unit formula (R 1 3SiO1/2)a(R 1 2SiO2/2)b(R 1 HSiO2/2)c, where R 1 is as described above; a = 2; b = 3.4 to 57; c = 3.3 to 50; and a quantity (b + c) = 6.7 to 101.
  14. 14. An alkenyloxy-, phenyl- terminated glycol ether of formula: D has empirical formula -C 2 H 4 - or -C 3 H 6 -; and subscript n is 1, 2, or 3; with the proviso that when X = H and D = -C2H4-, then subscript n is 2 or 3.
  15. 15. The alkenyloxy-, phenyl- terminated glycol ether of claim 14, wherein the alkenyloxy-, phenyl- terminated glycol ether is 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)propoxy)benzene; (2-(2-((2-methylallyl)oxy)ethoxy)ethoxy)benzene; and (2-(2-((2-methylallyl)oxy)propoxy)propoxy)benzene.

Description

SILICONE - POLYETHER COPOLYMER AND METHOD FOR SYNTHESIS THEREOF CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63/525185 filed on July 6, 2023, under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No.63/525185 is hereby incorporated by reference. FIELD [0002] This invention relates to a silicone - polyether copolymer (SPE copolymer) and methods for its synthesis and use. INTRODUCTION [0003] Silicone - polyether copolymers (SPE copolymers) find use in a myriad of applications, such as wetting agents, thickeners, or surfactants. SPE copolymers find use in coatings and polyurethane foams. SPE copolymers have been used in personal care compositions, such as those described in U.S. Patent 4,265,878 to Keil and U.S. Patent 5,387,417 to Rentsch. There is an industry need for lower cost replacements for phenyl functional siloxanes for such applications. SUMMARY [0004] A silicone - polyether copolymer (SPE copolymer) is provided. A method for synthesizing the SPE copolymer is also provided. DETAILED DESCRIPTION [0005] The method for synthesizing the SPE copolymer, introduced above, comprises: 1) combining, under conditions to effect hydrosilylation reaction, starting materials comprising A) an alkenyloxy-, aryl- terminated glycol ether, B) a polyorganohydrogensiloxane, and C) a hydrosilylation reaction catalyst. The starting materials may optionally further comprise D) an alkenyl-functional aromatic compound that differs from A) the alkenyloxy-, aryl- terminated glycol ether, E) a dialkenyl-terminated siloxane oligomer, F) a solvent, or a combination of two or more of D), E), and F). [0006] Step 1) may be performed by any convenient means in any convenient equipment. For example, when the method will be performed in a batch mode, a reactor with heating and cooling means (such as a jacket containing water or other heat transfer fluid) and mixing means (such as baffles and/or an agitator) may be used. One or more of the starting materials may be combined in the reactor, and thereafter the remaining starting materials may be added, either all at once, or metering into the reactor continuously or intermittently in aliquots. For example, starting materials with alkenyl groups, such as A) the alkenyloxy-, aryl- terminated glycol ether and when used D) the alkenyl-functional aromatic compound and/or E) the dialkenyl-terminated siloxane oligomer may be combined with B) the polyorganohydrogensiloxane, and thereafter all or a portion of C) the hydrosilylation reaction catalyst may be added. Additional portions of alkenyl-functional starting materials and C) hydrosilylation reaction catalyst may be added one or more times until the silicon bonded hydrogen atoms of B) the polyorganohydrogensiloxane have reacted with alkenyl groups. [0007] Alternatively, starting materials with alkenyl groups, such as A) the alkenyloxy-, aryl- terminated glycol ether and when used D) the alkenyl-functional aromatic compound and/or E) dialkenyl-terminated siloxane oligomer may be combined with all or a portion of C) the hydrosilylation reaction catalyst in the reactor. Thereafter, B) the polyorganohydrogensiloxane may be added continuously or intermittently with heating or cooling to control the reaction rate. Without wishing to be bound by theory, when the hydrosilylation reaction is performed on a commercial scale, it may be desirable to separate B) the polyorganohydrogensiloxane and C) the hydrosilylation reaction catalyst until just before reaction with the alkenyl-functional starting materials for safety reasons. [0008] The hydrosilylation reaction in step 1) may be performed at a temperature of 50 °C to 150 °C for a time sufficient to react all of the silicon bonded hydrogen atoms of starting material B) with an alkenyl group of starting material A) (and when present, starting material D) and/or starting material E)). [0009] The method may optionally further comprise one or more additional steps. For example, one or more of the starting materials may optionally be dissolved in F) the solvent before or during step 1). For example, C) the hydrosilylation reaction catalyst may be dissolved in F) the solvent before combining with the other starting materials used in step 1). The method may optionally further comprise step 2) recovering the SPE copolymer. Recovering may be performed by any convenient means, such as one or more of: color removal (e.g., via treating the reaction product comprising the SPE copolymer prepared in step 1) with an adsorbent such as activated carbon, either batchwise or continuously by passing the reaction product through a packed bed of activated carbon); filtration (e.g., to remove activated carbon in the batchwise process and/or other particulate); and/or stripping and/or distillation (e.g., to remove solvent, when used, a side product of the hydrosilylation reaction, if any, such as an isomerization product, and/o