WO2023102167A1 - Production d'hydroxydes d'ammonium quaternaire anhydres - Google Patents

Production d'hydroxydes d'ammonium quaternaire anhydres Download PDF

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Publication number
WO2023102167A1
WO2023102167A1 PCT/US2022/051625 US2022051625W WO2023102167A1 WO 2023102167 A1 WO2023102167 A1 WO 2023102167A1 US 2022051625 W US2022051625 W US 2022051625W WO 2023102167 A1 WO2023102167 A1 WO 2023102167A1
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WO
WIPO (PCT)
Prior art keywords
quaternary ammonium
oxide
ammonium hydroxide
anhydrous
anhydrous quaternary
Prior art date
Application number
PCT/US2022/051625
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English (en)
Inventor
Hui Zhou
Ke Zhang
Original Assignee
Huntsman Petrochemical Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Petrochemical Llc filed Critical Huntsman Petrochemical Llc
Publication of WO2023102167A1 publication Critical patent/WO2023102167A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins

Definitions

  • the present disclosure generally relates to a method for the production of anhydrous quaternary ammonium hydroxides. More specifically, the present disclosure relates to the synthesis of anhydrous quaternary ammonium hydroxides by the addition reaction of alkylene oxide to tertiary amines for electronic applications, such as cleaning, stripping, or etching formulations.
  • aqueous quaternary ammonium compounds such as, tetramethylammonium hydroxide (TMAH), choline hydroxide, etc.
  • TMAH tetramethylammonium hydroxide
  • Aqueous formulations can cause watermarks (drying spots) to form during the drying process.
  • Solvent based formulations have been reported and used to reduce watermarks, however, such formulations can be limiting due to solvent incompatibility.
  • anhydrous quaternary ammonium hydroxide can provide users with more options for their formulations.
  • Such anhydrous quaternary ammonium hydroxides can be formulated in either water- or solvent-based applications.
  • compositions and/or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those having ordinary skill in the art that variations may be applied to the compositions and/or methods and in the steps or sequences of steps of the methods described herein without departing from the concept, spirit, and scope of the present disclosure. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure.
  • the term “about” is used to indicate that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject(s) to be measured.
  • the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.
  • At least one will be understood to include one as well as any quantity more than one, including but not limited to, 1 , 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.
  • the term “at least one” may extend up to 100 or 1000 or more depending on the term to which it refers.
  • the quantities of 100/1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results
  • the phrase “at least one of X, Y, and Z” will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z.
  • the phrase “at least one of X and Y” will be understood to include X alone, Y alone, as well as any combination of X and Y.
  • the phrase “at least one of” can be used with any number of components and have the similar meanings as set forth above.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • % by weight As used herein, the terms “% by weight”, “wt %”, “weight percentage”, or “percentage by weight” are used interchangeably.
  • ambient temperature refers to the temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the curable composition is used), exclusive of any temperature changes that occur as a result of the direct application of heat to the curable composition to facilitate curing.
  • the ambient temperature is typically between about 10°C and about 30°C, more specifically about 15°C and about 25°C.
  • anhydrous quaternary ammonium hydroxide which can be used in either water- or solvent-based applications.
  • the processes described herein can be used to prepare an anhydrous quaternary ammonium hydroxide compound having the formula (NR 1 R 2 R 3 R 4 )OH, wherein R 1 , R 2 , R 3 and R 4 are the same as or different from one another and are each individually selected from H, C1-C10 alkyls including linear or cyclo alkyls, C1-C10 hydroxylalkyls, and C6-C12 aryls.
  • the processes described herein can include reacting an alkylene oxide with a tertiary amine having the formula R1 R2R3N, wherein R1 , R2 and R3 are the same as or different from one another and are each individually selected from C1-C10 alkyls including linear or cyclo alkyls, C1-C10 hydroxyalkyls, and C6-C12 aryls, to yield the anhydrous quaternary ammonium hydroxide.
  • the reaction of alkylene oxide and tertiary amine can be performed in an aqueous environment.
  • reaction can be performed in an anhydrous environment using one or more solvents including, without limitation, N- methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, t-butyl alcohol, ethylene glycol, and propylene glycol.
  • solvents including, without limitation, N- methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, t-butyl alcohol, ethylene glycol, and propylene glycol.
  • Alkylene oxides which can be used to produce the presently disclosed anhydrous quaternary ammonium hydroxide can include, without limitation, ethylene oxide, propylene oxide, butylene oxide, allyl glycidyl ether, hexene oxide, styrene oxide, epichlorohydrin, cyclohexene oxide, spiro-epoxy oxindole, and the like.
  • Tertiary amines which can be used to produce the presently disclosed anhydrous quaternary ammonium hydroxide can include, without limitation, trimethylamine, triethylamine, tripropylamine, tributlylam ine, triocylamine, dimethylethylamine, diethylmethylamine, dimethylbenzylamine, dimethylaniline, dimethylcyclohexylamine, diethylbenzylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, dimethylpropanolamine, diethylethanolamine, ethyldiethanolamine, and methylethylpropanolamine.
  • Byproducts of the presently process can include water and unreacted amine.
  • the amount of water generated as a byproduct of the reaction can be maintained at extremely low levels.
  • the water generated as a byproduct can be controlled at less than about 5% by weight.
  • the water generated as a byproduct can be controlled at less than about 1 % by weight.
  • the molar ratio of alkylene oxide to tertiary amine present in the reaction described herein ranges from about 6:1 to about 1 :3, preferably from about 4: 1 to about 1 :2, and more preferably from about 2: 1 to about 1 :1.
  • the reaction can be performed at a temperature range of from about ambient temperature to about 70°C. In at least one example, the reaction temperature can range from about 30°C to about 60°C. The reaction can be performed at a pressure of less than about 60 psi. In at least one example, the reaction pressure can be less than about 55 psi.
  • the quaternary ammonium hydroxides produced by the methods described herein can provide a better EHS profile including, without limitation, lower toxicity as compared to those conventionally made using tetramethylammonium hydroxide (TMAH) or choline hydroxide. For example, TMAH is commonly used at a 2.38% by weight aqueous solution, which has high levels of toxic materials.
  • Formulation requirements for etching and cleaning different metals, photoresist, organics can vary for analog, logic, dynamic random access memory (DRAM), NAND semiconductor devices, as well as display and photovoltaic devices can vary drastically.
  • concentration of the starting materials can be adjusted to achieve a desired strength of the resulting anhydrous quaternary ammonium hydroxide.
  • changing the tertiary amines precursor structure can allow the anhydrous quaternary ammonium hydroxide etching capability and hydrophilicity to be tailored for specific end uses.
  • the processes can therefore enable the formation of a variety of anhydrous quaternary ammonium hydroxide formulas for various uses including, without limitation, etching, stripping, and cleaning purposes.
  • the final formulations can be either water- or solvent-based.
  • anhydrous quaternary ammonium hydroxide which can have increased freedom in formulation design for a specific wet processing step, such as a specific type or mixture of metal/sem iconductor surfaces, nature of prior processing residues, or a certain effect on a surface is desired.
  • a final formulation can be created with water or a solvent.
  • solvent can be an isopropyl alcohol or an ethylene oxide reactive solvent.
  • Example 1 [0032] In a clean and dry 8-gallon kettle equipped with an agitator and nitrogen line, 6.33 pounds (lbs) methyldiethanolamine and 0.53 lb water were charged and padded with nitrogen. With the cooling on, ethylene oxide was introduced at ambient temperature and pressure. The temperature was maintained at 30°C. The addition rate of ethylene oxide must be low initially, but can be ramped up gradually in order to maintain the reaction temperature. After 1.25 lbs of ethylene oxide was added, the digestion was continued for 1 hour at 50 psi max. The kettle can be slowly vented while nitrogen can be used to strip the residual ethylene oxide to the scrubber for 1 hour. Under minimized air contact, 0.064 lb of stabilizer was added under nitrogen. After fully mixed, the final product was discharged into a plastic container.
  • Titration of the final product indicated about 42% by weight quaternary ammonium hydroxides, 2% by weight free water and excess methyldiethanolamine.
  • the pH of the final product was determined to be about 12.9.
  • Titration of the final product indicated about 54% by weight quaternary ammonium hydroxides, 3% by weight free water and excess methyldiethanolamine.
  • the pH of the final product was determined to be about 13.
  • Titration of the final product indicated about 69% by weight quaternary ammonium hydroxides and excess methyldiethanolamine. No free water was detected The pH of the final product was determined to be about 13. The product is very high viscosity, paste like liquid.

Abstract

L'invention concerne un procédé de synthèse d'hydroxydes d'ammonium quaternaire anhydres ayant la formule (NR1R2R3R4)OH, dans laquelle R1, R2, R3 et R4 sont identiques ou différents les uns des autres et sont chacun individuellement choisis parmi H, les alkyles en C1-C10 comprenant des alkyles linéaires ou cycliques, et les aryles en C6-C12 par réaction d'un oxyde d'alkylène avec une amine tertiaire de formule R1R2R3N dans laquelle R1, R2 et R3 sont identiques ou différents et sont chacun individuellement choisis parmi les alkyles en C1-C10 comprenant des alkyles linéaires et cycliques, les hydroxyalkyles en C1-C10, les aryles en C6-C12 et des formulations ayant des hydroxydes d'ammonium quaternaire anhydres.
PCT/US2022/051625 2021-12-03 2022-12-02 Production d'hydroxydes d'ammonium quaternaire anhydres WO2023102167A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163285787P 2021-12-03 2021-12-03
US63/285,787 2021-12-03

Publications (1)

Publication Number Publication Date
WO2023102167A1 true WO2023102167A1 (fr) 2023-06-08

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991001295A1 (fr) * 1989-07-17 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de composes quaternaires de l'ammonium
US5840177A (en) * 1994-03-03 1998-11-24 Baker Hughes Incorporated Quaternary ammonium hydroxides as mercaptan scavengers
US20130190534A1 (en) * 2012-01-19 2013-07-25 Dow Agrosciences Llc Process for preparing choline hydroxide from trimethylamine and ethylene oxide
US20130261039A1 (en) * 2012-03-27 2013-10-03 Sachem, Inc. Quaternary ammonium hydroxides
US20150031917A1 (en) * 2011-12-29 2015-01-29 Taminco Process for the production of choline hydroxide
US20160068476A1 (en) * 2013-04-11 2016-03-10 Taminco Process for choline hydroxide
US20210179972A1 (en) * 2018-08-30 2021-06-17 Huntsman Petrochemical Llc Quarternary ammonium hydroxides of polyamines

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991001295A1 (fr) * 1989-07-17 1991-02-07 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de composes quaternaires de l'ammonium
US5840177A (en) * 1994-03-03 1998-11-24 Baker Hughes Incorporated Quaternary ammonium hydroxides as mercaptan scavengers
US20150031917A1 (en) * 2011-12-29 2015-01-29 Taminco Process for the production of choline hydroxide
US20130190534A1 (en) * 2012-01-19 2013-07-25 Dow Agrosciences Llc Process for preparing choline hydroxide from trimethylamine and ethylene oxide
US20130261039A1 (en) * 2012-03-27 2013-10-03 Sachem, Inc. Quaternary ammonium hydroxides
US20160068476A1 (en) * 2013-04-11 2016-03-10 Taminco Process for choline hydroxide
US20210179972A1 (en) * 2018-08-30 2021-06-17 Huntsman Petrochemical Llc Quarternary ammonium hydroxides of polyamines

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