WO2004018401A1 - Preparation de bisphenols par couplage oxydatif d'alkylphenols au moyen d'un catalyseur de cuivre recyclable - Google Patents

Preparation de bisphenols par couplage oxydatif d'alkylphenols au moyen d'un catalyseur de cuivre recyclable Download PDF

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Publication number
WO2004018401A1
WO2004018401A1 PCT/US2002/027221 US0227221W WO2004018401A1 WO 2004018401 A1 WO2004018401 A1 WO 2004018401A1 US 0227221 W US0227221 W US 0227221W WO 2004018401 A1 WO2004018401 A1 WO 2004018401A1
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WIPO (PCT)
Prior art keywords
dialkylphenol
copper
solvent
oxygen
complex
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PCT/US2002/027221
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English (en)
Inventor
Gregory Kaplan
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Wiley Organics, Inc.
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Priority to AU2002329866A priority Critical patent/AU2002329866A1/en
Priority to PCT/US2002/027221 priority patent/WO2004018401A1/fr
Publication of WO2004018401A1 publication Critical patent/WO2004018401A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/65—Metal complexes of amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a method for producing biphenols by oxidative coupling of dialkylphenols. More particularly it is directed to a method which proceeds in two stages using a copper amine complex which is catalytically effective in each stage. Still more particularly it relates to a novel copper amine complex with high catalytic activity for the oxidative coupling of substituted phenols under mild conditions which has dual (two stage) activity and can be readily recycled and reused. Still more particularly it relates to the method of reactivating the catalyst, which can be decomposed by exposure to elevated temperatures or interaction with other chemicals.
  • the invention is a process for producing tetraalkylbiphenols and, more particularly, 2,2',6,6'-tetraalkyl-4,4'-biphenols by the stepwise oxidative coupling of 2,4-dialkylphenols or 2,6-dialkylphenols in the presence of a copper amine complex.
  • the reaction of the 2,6- dialkylphenols is preferred.
  • the first step of this reaction is the synthesis of 3,3 ',5,5'- tetraalkyl-4,4'-diphenoquinones using oxygen as an oxidizer to couple the 2,6- dialkylphenols.
  • the second step is the synthesis of 2,2',6,6'-tetraalkyl-4,4'-biphenols using 3,3',5,5'-tetraalkyl-4,4'-diphenoquinones as an oxidizer to couple 2,6-dialkylphenols.
  • Both steps usually employ an excess of the phenol.
  • the same catalyst can be used in both steps.
  • the reaction proceeds under extremely mild conditions used in the preferred embodiments of the invention and this results in highly selective syntheses in both steps.
  • the extremely high activity of the catalytic system used in the preferred embodiment of the invention enables the use of only a very modest amount (i.e. about 0.05 to 1% based on dialkylphenol) of catalyst.
  • the oxidation proceeds well at modest concentrations of oxygen; thus headspace air pressures as low as 1 to 100 psi are useful and high pressures for oxygenation are not required.
  • the catalyst is readily removed from the product stream and recovered for reuse. Typically, essentially no impurities are produced.
  • the system described below also can permit the efficient recovery of any unreacted 2,6-dialkylphenol starting materials, permitting their reuse without subsequent additional purification.
  • 2,2',6,6'-tetraalkyl-4,4'-biphenols can be efficiently produced in a two-step process by using a copper-amino salt complex with dual catalytic activity and two oxidizing agents, first oxygen, then the corresponding 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone intermediate, to couple 2,6-dialkylphenols.
  • the process utilizes a solvent, which significantly reduces the temperature at which the coupling occurs, permitting high selectivity to be achieved.
  • the solvent permits the recovery of excess 2,6-dialkylphenol and catalyst for reuse without subsequent additional purification.
  • the catalyst has improved catalytic activity compared to a similar system described in U.S. Pat 4,851,589. Unlike the catalyst described in that patent, the catalyst preferably used in the present invention, does not require an activation period, the use of acidic phenols, and can be removed from the products while retaining its full activity and reused. In addition, the catalyst can be prepared, recovered and stored in closed containers for over one year while retaining full catalytic activity, eliminating the need to prepare fresh catalyst for each reaction.
  • tetraalkylbiphenols are dealkylated to produce a 4,4'-biphenol and its analogs.
  • this reaction is conducted in the presence of a low boiling solvent to enhance and facilitate the removal of isobutylene and prevent the formation of polyisobutylene.
  • the catalyst is prepared by reacting a copper halide (e.g., cuprous bromide, cupric chloride, cupric bromide, and preferably cuprous chloride (CuCl)), with a tetraalkylalkylenediamine.
  • a copper halide e.g., cuprous bromide, cupric chloride, cupric bromide, and preferably cuprous chloride (CuCl)
  • CuCl cuprous chloride
  • the preferred diamine is N,N,N',N'-tetramethylethylenediamine (TMEDA), but other diamines that have been used in the preparation of copper amine complexes could also be used such as all ylamines, dialkylamines, arylamines, pyridines, etc.
  • the copper-amino complex is prepared under aerobic conditions in the polar organic solvents such as acetone, tetrahydrofuran (THF), alkyl esters such as ethyl acetate, butyl acetate etc., other ketones such as methyl ethyl ketone (MEK), etc., and ethers such as dimethyl ether, methyl-t-butyl ether (MTBE), etc.
  • solvents are selected because the catalyst is essentially insoluble and precipitates as a dark brown solid.
  • the catalyst clearly differs in its properties from the catalyst described in the U.S. Pat 4,851,589.
  • the invention is not limited to the use of the preferred copper-amino complex.
  • Known copper-amino complexes can also be adapted for use in the two stage dual catalytic reaction of 2,6-dialkylphenols as described herein.
  • the 2,6-dialkylphenol to be coupled is dissolved in methanol. While methanol is clearly the preferred solvent, those skilled in the art will recognize that other solvents, in particular other alcohols such as ethanol, isopropanol or butanol can be used.
  • a solvent is selected which dissolves the dialkylphenol and the catalyst and water. It is also important to be able to remove water from this solvent, if it is to be reused in the next cycle. In addition to alcohols, ketones may also be useful.
  • the concentration of the 2,6-dialkylphenol is typically about 1 to 5 molar.
  • An excess of the phenol is used for the reaction.
  • As little as 0.05% by weight of catalyst based on phenol can be effective and is added to the solution of the phenol.
  • the preferred catalyst is completely soluble in the methanolic solution of the 2,6-dialkylphenol.
  • Oxygen or air is bubbled directly into reaction mixture, or is delivered to the headspace of the reactor at a modest pressure (i.e., about 5 to 20 psi air).
  • the amount of oxygen is readily determined based on the stoichiometry of the reaction.
  • the temperature of the reaction can be easily and preferably controlled in the range of about 30 to 50°C. Higher temperatures can be used particularly with solvents having a higher boiling point than methanol but in the interest of maintaining the selectivity of the reaction lower temperatures are preferred.
  • Methanol serves several of important purposes: it keeps the viscosity of the reaction mixture low while the 3,3',5,5'-tetraalkyl-4,4'-diphenoquinones are being produced, affording ease of agitation and efficient mixing; it freely dissolves water, the byproduct of reaction, keeping the catalyst active; methanol is also used to separate the catalyst and excess 2,6-dialkylphenol from the final product for reuse in subsequent reactions.
  • oxygen addition may be stopped and reaction carried out in the absence of oxygen.
  • the methanol solvent is removed by distillation for re-use, then the water produced as a by-product of the reaction is removed by distillation at a higher temperature and disposed of.
  • the temperature needs to be raised just enough to keep reaction mixture in a liquid form, typically about 1 0 to 160°C.
  • the presence of the catalyst permits the intermediate 3,3',5,5'-tetraalkyl-4,4'-diphenoquinones to serve as oxidizing agents for the subsequent coupling of the 2,6-dialkylphenols.
  • Higher temperatures may be used if higher concentrations of diphenoquinone are used but it is not desirable to exceed temperatures of 200°C because catalyst will thermally decompose and dealkylation may occur.
  • the reaction mixture After the 3,3',5,5'-tetraalkyl-4,4'-diphenoquinone is consumed, the reaction mixture generally contains about 70 to 80% 2,2',6,6'-tetraalkyl-4,4'-biphenols and 20 to 30% 2,6-dialkylphenols.
  • reaction mixture is then cooled to approximately 60°C and the methanol that was removed by distillation is added back to the reaction mixture.
  • Additional diamine can be added at this time in order to regenerate any catalyst which may have decomposed. Typically from about 50% to 250% by weight of the molar equivalent of the diamine used in the preparation of the corresponding amount of copper-amino complex initially utilized in the reaction will be sufficient to regenerate the catalyst.
  • the 2,2',6,6'-tetraalkyl- 4,4 '-biphenols precipitate completely and can be removed by filtration or centrifugation, while the 2,6-dialkylphenols and the active catalyst remain in the filtrate or centrate.
  • these mother-liquors can be re-used to start another cycle of producing of 2,2',6,6'-tetraalkyl- 4,4 '-biphenols.
  • This method also facilitates removal of metal impurities from both the final product and waste streams. Reducing the amount of copper in the final product reduces undesirable color and conductivity; the latter is particularly important in the microelectronics applications.
  • Rl is an alkyl group having 1 to 6 carbons
  • R2 is alkyl group having 3 to 6 carbons.
  • one of the alkyl groups should have at least three carbon atoms to provide steric hindrance with respect to the phenolic oxygen atom and thereby prevent reaction. While the principal focus of the invention is on the preparation of tetraalkylbiphenols, Rl and R2 could also be Cl to C6 alkoxy moeities.
  • catalytic system described in this patent can also be employed in the one-step oxidative coupling of 2,4-dialkylphenols: + H2O
  • Rl and R2 are alkyl groups having 3 to 6 carbons. In the case of Rl or R2 having less then 3 carbons, C-O coupling will occur and the process will produce a mixture of C-O coupled oligomers.
  • This reaction does not proceed through the quinone, but otherwise this reaction proceeds under conditions which are substantially the same as those disclosed above for the first stage reaction of the 2,6-dialkylphenol.
  • the reaction is typically conducted using the temperatures, solvents and concentrations described herein for the first stage reaction.
  • the catalytic system described in this patent can also be employed in the one-step oxidation of 2,2',6,6'-tetraalkyl-4,4'-biphenols.
  • R1-R2 are alkyl group having 1 to 6 carbons.
  • the reaction is typically conducted using the temperatures, solvents and concentrations described herein for the first stage reaction. Catalyst may be suspended in the reaction mixture.
  • 4,4'-Biphenol can be produced from 2,2',6,6'-tetra- t-butyl-4,4'-biphenol through dealkylation.
  • a method of dealkylation which permits essentially complete dealkylation to be achieved at comparatively low temperatures while permitting recovery of more than 90% of isobutylene with high purity, e.g., exceeding 99.5%.
  • the 4,4'-biphenol produced typically has a purity exceeding 99.5% without recourse to further purification by crystallization or distillation.
  • the method of dealkylation comprises the use of a strong acid and a solvent mixture in which a minimum of one component has a boiling point about 20 to 50°C lower then the temperature of the reaction mixture.
  • the dealkylation reaction is usually carried out at a temperature of about 130 to 170°C.
  • the low boiling solvent are hydrocarbons with 7-9 carbons, halogenated hydrocarbons with boiling point about 80 to 130°C.
  • Preferably about 5 to 30 % by volume of the solvent mixture is a low boiling solvent.
  • the use of this solvent mixture keeps the reaction mixture saturated with vapors of this low- boiling component and very efficiently removes isobutylene from the reaction mixture before it polymerizes or alkylates the solvent or the biphenols in the reaction mixture.
  • acids that can be used in the dealkylation include sulfonic acids such as methanesulfonic acid, which is preferred, sulfuric acid, toluenesulfonic acid, aluminum phenoxides etc.
  • Example 1 The invention is illustrated in more detail by the following non-limiting examples.
  • Example 1 The invention is illustrated in more detail by the following non-limiting examples.
  • Catalyst Preparation 20 grams of cuprous chloride (CuCl) and 40 grams of tetramethylethylenediamine (TMEDA) are stirred at room temperature in 200 ml of acetone for 3 hours under aerobic conditions (i.e. no attempt is made to exclude atmospheric oxygen). A dark brown solid precipitates and is recovered by filtration, washed with 50 ml of acetone, and dried in the presence of air. 45 grams of catalyst is collected.
  • CuCl cuprous chloride
  • TMEDA tetramethylethylenediamine
  • reaction mixture contains about 35% of 3,3',5,5'-tetra-t-butyl-4,4'-diphenoquinone and about 65% of unreacted 2,6-di-t-butylphenol.
  • Methanol and water are distilled off and the temperature is raised to 150-160°C under nitrogen blanket.
  • reaction mixture contains approximately 70% 2,2',6,6'-tetra-t-butyl-4,4'-biphenol and approximately 30% unreacted 2,6-di-t-butylphenol.
  • the reaction mixture is cooled to 60°C and 200 ml of the methanol that was previously distilled off is added. 0.3 grams of the TMEDA is added. The mixture is then cooled to 25°C and filtered.
  • the filter cake is washed with an additional 50 ml of methanol and air-dried overnight.
  • the dried solids have a mass of 297 grams (70% of theoretical yield of 2,2'6,6'-tetra-t-butyl-4,4'-biphenol). 297 grams of fresh 2,6-di-t-butylphenol is added to the mother liquor containing the catalyst and 127 grams of unreacted 2,6-di-t-butylphenol and the cycle is repeated.
  • the filter cake is washed with an additional 50 ml of methanol and air dried overnight.
  • the mass of the dried filter cake has a mass of 280 gm (72% of the theoretical yield of 2,2'-dimethyl-6,6'-di-t-butyl-4,4'-biphenol).
  • Additional 100 gm of 2,2'-dimethyl-6,6'-di-t-butyl-4,4'-biphenol along with 10 gm of unreacted 2-methyl-6-t- butylphenol and the catalyst remained in the mother liquor been recovered.
  • TMBP 2,2',6,6'-tetramethyl-4,4'-biphenol
  • the mixture is stirred for 2 hours at a temperature of 45-46 °C, then cooled to 35°C and filtered.
  • the filter cake is washed with 2 liters of methanol, then air-dried overnight.
  • the mass of the dried filter cake is 1,650 grams (82.5% of theoretical yield of 4,4',6,6'-tetra-t-butyl-2,2'-biphenol).
  • the mother liquor is distilled until its volume is reduced to 800 ml, whereupon an additional 85 grams of 4,4',6,6'-tetra-t-butyl-2,2'-biphenol is collected by filtration.
  • the remaining mother liquor containing unreacted 2,4-di-t-butyl ⁇ henol and catalyst is reused in another cycle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé servant à préparer des bisphénols par couplage oxydatif de dialkylphénols en deux étapes au moyen d'un complexe cuivre-amine exerçant une action catalytique à chaque étape. L'invention concerne également un nouveau complexe cuivre-amine exerçant une activité catalytique importante dans le couplage oxydatif de phénols substitués dans des conditions non agressives, possédant une activité double (deux stades) et pouvant être recyclé et réutilisé immédiatement.
PCT/US2002/027221 2002-08-26 2002-08-26 Preparation de bisphenols par couplage oxydatif d'alkylphenols au moyen d'un catalyseur de cuivre recyclable WO2004018401A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002329866A AU2002329866A1 (en) 2002-08-26 2002-08-26 Preparation of biphenols by oxidative coupling of alkylphenols using a recyclable copper catalyst
PCT/US2002/027221 WO2004018401A1 (fr) 2002-08-26 2002-08-26 Preparation de bisphenols par couplage oxydatif d'alkylphenols au moyen d'un catalyseur de cuivre recyclable

Applications Claiming Priority (1)

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PCT/US2002/027221 WO2004018401A1 (fr) 2002-08-26 2002-08-26 Preparation de bisphenols par couplage oxydatif d'alkylphenols au moyen d'un catalyseur de cuivre recyclable

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115611709A (zh) * 2022-12-15 2023-01-17 北京弗莱明科技有限公司 一种4,4’-二羟基联苯的合成方法
CN116444349A (zh) * 2023-06-19 2023-07-18 北京弗莱明科技有限公司 一种3,3',5,5'-四烷基-4,4'-联苯二酚的制备方法
CN116640048A (zh) * 2023-05-29 2023-08-25 江苏新瀚新材料股份有限公司 一种4,4’-联苯二酚的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306874A (en) * 1962-07-24 1967-02-28 Gen Electric Oxidation of phenols
US4028341A (en) * 1974-02-11 1977-06-07 General Electric Company Process for the preparation of polyphenylene oxides with hydrolytically stable copper catalysts
US4132722A (en) * 1976-11-26 1979-01-02 Ici Americas Inc. Oxidative coupling of alkylphenols catalyzed by metal complexes of diimino acid
US4319544A (en) * 1980-11-24 1982-03-16 Coulter Systems Corporation Digitally synthesized dynamic bias method and apparatus for toning control in developing latent electrophotographic images
US4851589A (en) * 1987-09-18 1989-07-25 Amoco Corporation Oxidative coupling of alkylphenols by copper catalysts
US4965384A (en) * 1987-09-18 1990-10-23 Amoco Corporation Production of copper amine salt complexes for catalysts for the oxidative coupling of alkylphenols

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3306874A (en) * 1962-07-24 1967-02-28 Gen Electric Oxidation of phenols
US4028341A (en) * 1974-02-11 1977-06-07 General Electric Company Process for the preparation of polyphenylene oxides with hydrolytically stable copper catalysts
US4132722A (en) * 1976-11-26 1979-01-02 Ici Americas Inc. Oxidative coupling of alkylphenols catalyzed by metal complexes of diimino acid
US4319544A (en) * 1980-11-24 1982-03-16 Coulter Systems Corporation Digitally synthesized dynamic bias method and apparatus for toning control in developing latent electrophotographic images
US4851589A (en) * 1987-09-18 1989-07-25 Amoco Corporation Oxidative coupling of alkylphenols by copper catalysts
US4965384A (en) * 1987-09-18 1990-10-23 Amoco Corporation Production of copper amine salt complexes for catalysts for the oxidative coupling of alkylphenols

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115611709A (zh) * 2022-12-15 2023-01-17 北京弗莱明科技有限公司 一种4,4’-二羟基联苯的合成方法
CN116640048A (zh) * 2023-05-29 2023-08-25 江苏新瀚新材料股份有限公司 一种4,4’-联苯二酚的制备方法
CN116640048B (zh) * 2023-05-29 2023-10-24 江苏新瀚新材料股份有限公司 一种4,4’-联苯二酚的制备方法
CN116444349A (zh) * 2023-06-19 2023-07-18 北京弗莱明科技有限公司 一种3,3',5,5'-四烷基-4,4'-联苯二酚的制备方法

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