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WO-2026096846-A1 - ALKOXYLATIONS USING POLYHEDRAL BORATE CATALYSTS

WO2026096846A1WO 2026096846 A1WO2026096846 A1WO 2026096846A1WO-2026096846-A1

Abstract

Alkoxylations are performed by combining an alkylene oxide with a starter and a polyhedral borate catalyst. The polyhedral borate catalyst has the form [Cat + ] n [B 12 X u Y v ] n- and/or [Cat + ] m [B 10 X w Y z ] m- . The polyhedral borate catalysts are extremely active and therefore produce very high alkoxylation rates. When used to polymerize propylene oxide, the catalysts produce alkoxylated products that have high proportions of primary hydroxyl groups.

Inventors

  • KENNEDY, Robert Daniel
  • AXTELL, Jonathan

Assignees

  • DOW GLOBAL TECHNOLOGIES LLC

Dates

Publication Date
20260507
Application Date
20251031
Priority Date
20241031

Claims (20)

  1. CLAIMS
  2. What is claimed is:
  3. 1. A method for producing an alkoxylate, the method comprising:
  4. combining (1) a polyhedral borate, (2) at least one starter, and (3) at least one alkylene oxide; and
  5. subjecting the resulting combination to alkoxylation conditions such that the starter and alkylene oxide react to produce an alkoxylate;
  6. wherein the polyhedral borate comprises
  7. [Cat + ] n [B 12 X u Y v ] n - and/or [Cat + ] m [B 10 X w Y z ] m -,
  8. where
  9. Cat + is a proton or a protonated neutral molecule, each X is independently selected from hydrogen, halogen; C-^Q hydrocarbyl, which is optionally substituted with halogen; -OH, -OR -SH, -SR cyanide, nitrite or triflate, each Y is independently selected from NH 3 ,
  10. cyclic thioether, cyclic dithioether, O(R^) 2 , cyclic ether, cyclic diether, O=S(R^) 2 , S(O) 2 (R^) 2 , and O=P(R1) 3 , where each R^ is independently C-|_ 3 5 hydrocarbyl, which is optionally substituted with halogen, v is 0 or 1, n is (2-v), u is (12-v), z is 0 or 1, m is (2-z), and w is (10-z).
  11. 2. The method of claim 1, wherein each X is independently hydrogen, halogen or hydroxyl.
  12. 3. The method of claim 1, wherein the polyhedral borate is one or more of [Cat + ] 2 [B 12 H 12 ] 2 -- ZH 2 O, [Cat + ] 2 [B 12 F 12 ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 CI 12 ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Br 12 ] 2 - • ZH 2 O, ZH 2 O, [Cat + ] 2 [B 12 I 12 ] 2 ' • ZH 2 O,
  13. [Cat + ] 2 [B 12 (OH) 12 ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 H a F 12.a ] 2 - • ZH 2 O,
  14. [Cat + ] 2 [B 12 H a CI 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 H a Br 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 H a l 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 H a (OH) 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 F a CI 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 F a Br 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 F a l 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 F a (OH) 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Cl a Br 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Cl a l 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Cl a (OH) 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Br a l 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 Br a (OH) 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 12 l a (OH) 12.a ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 F 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 CI 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Br 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 l 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 (OH) 10 ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H b F 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H b CI 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H b Br 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H b l 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 H b (OH) 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 F b CI 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 F b Br 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 F b l 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 F b (OH) 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Cl b Br 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Cl b l 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Cl b (OH) 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Br b l 10.b ] 2 - • ZH 2 O, [Cat + ] 2 [B 10 Br b (OH) 10.b ] 2 - • ZH 2 O,
  15. each a is 1 to 11, each b is 1 to 9, and each Z is 0 to 12.
  16. 4. The method of claim 1 wherein the polyhedral borate is one or more of
  17. [Cat + ][B 12 l 11 (SR 1 2 )r • ZH 2 O, [Cat + ][B 10 H 9 (NR 1 3 )J- • ZH 2 O,
  18. [Cat + ][B 10 F 9 (NR 1 3 )]- • ZH 2 O, [Cat + ][B 10 CI 9 (NR 1 3 )]- • ZH 2 O,
  19. [Cat + ][B 10 Br 9 (NR 1 3 )J- • ZH 2 O, [Cat + ][B 10 l 9 (NR 1 3 )J- • ZH 2 O, [Cat + ][B 10 H 9 (PR 1 3 )r • ZH 2 O, [Cat + ][B 10 F 9 (PR 1 3 )]- • ZH 2 O,
  20. [Cat + ][B 10 CI 9 (PR 1 3 )r • ZH 2 O, [Cat + ][B 10 Br 9 (PR 1 3 )J- • ZH 2 O,

Description

ALKOXYLATIONS USING POLYHEDRAL BORATE CATALYSTS CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to and all advantages of U. S. provisional patent application no. 63/714,206 filed on 31 October 2024, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION [0002] This disclosure relates to a process for alkoxylating a starter compound with one or more alkylene oxides. DESCRIPTION OF THE RELATED ART [0003] Alkylene oxide polymers and copolymers are produced globally in large quantities. Polyether polyols, for example, are an important raw material for producing polyurethanes. Among other things, they are used to make high resiliency, molded, or rigid foams. Polyether monols are used, for example, as surfactants and industrial solvents, among other uses. Carbonate- and ester-modified alkylene oxide polymers also find uses in these and other applications. [0004] Polyether monols and polyols are produced by alkoxylating a starter compound by reaction with an alkylene oxide. The starter compound has one or more functional groups at which the alkylene oxide can react to produce a polyether. The main functions of the starter compound are to provide molecular weight control and to establish the number of hydroxyl groups the polyether will have. [0005] A catalyst is needed to obtain economical reaction rates. The most commonly used catalysts are alkali metal hydroxides such as potassium hydroxide and the so-called double metal cyanide (DMC) catalyst complexes, of which zinc hexacyanocobaltate catalyst complexes are the most commercially important type. [0006] Alkali metal hydroxides provide the benefits of low catalyst costs and acceptable reaction rates. They are versatile in that they effectively catalyze alkoxylations using many alkylene oxides. The product polyether usually, but not always, has a narrow molecular weight distribution. Nonetheless alkali metal hydroxides have well-known drawbacks. Alkali metal hydroxide catalysts promote a side reaction that forms unsaturated monoalcohols, which become alkoxylated to form unwanted monofunctional species. The presence of these unwanted monofunctional species can also broaden molecular weight distribution. Another drawback is that alkoxylated products made using these catalysts need to be neutralized and purified to remove catalyst residues, which adds significant capital and operating expense to the manufacturing process. [0007] DMC catalysts provide rapid reaction rates compared to alkali metal catalysts, even when used at very low catalyst concentrations. In addition, they have distinct and important advantages over alkali metal catalysts. The DMC catalysts rarely, if at all, promote the side reaction that produces monofunctional by-products, so the hydroxyl functionality of the product is close to the theoretical value (as defined by the starter). A second main advantage is that no neutralization step is needed. The catalyst residues often can be left in the product, unlike the case when alkali metal hydroxides are used as the polymerization catalyst. This can result in significantly lower production costs. Nonetheless, DMC catalysts have disadvantages as well. They perform poorly in the presence of high concentrations of hydroxyl groups, and especially in the presence of low molecular weight starter compounds like glycerin that have hydroxyl groups in the 1,2- or 1,3- positions with respect to each other. Therefore, DMC catalysts have not been found to be useful to produce low molecular weight polyethers. [0008] Various Lewis acids and Bronsted acids have been evaluated as polymerization catalysts. EP2691440B1 describes short-chain polyether polyols using a low molecular weight starter, using an acid catalyst and a DMC catalyst in sequence. Among the acids are Lewis acids such as boron trifluoride, antimony pentafluoride, phosphorus pentafluoride and Bronsted acids such as triflic acid, fluorosulfonic acid, fluoroantimonic acid, perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid and carborane (HCHB^CI-|i). Reaction in the presence of the acid catalyst produces a 50 to 200 equivalent weight intermediate that is further alkoxylated using a double metal cyanide catalyst to form the final product. US Pat. 8,680,211 describes using “superacids” to produce hybrid polyester-polyether polyols; carborane (HCHB^ ^Cl<| <|) appears in a list of superacid candidates. [0009] WO 2024/086488, WO 2024/086489, and WO 2024/086490 describe various phosphonium catalysts useful for alkoxylation reactions. The positively charged phosphonium cation is associated with a weakly coordinating anion, of which ®12®r12^- are mentioned. BRIEF SUMMARY [0010] This disclosure is in one aspect a method for producing an alkoxylate, the method comprising combining (1) a polyhedral borate, (2) at least one starter, and (3) at least one alkylene oxide, and subjecting the resulting combination to alkoxylation