WO1995011266A1 - PROCEDE POUR AUGMENTER LE NIVEAU DE α-GLYCOL DANS DES RESINES EPOXY LIQUIDES - Google Patents

PROCEDE POUR AUGMENTER LE NIVEAU DE α-GLYCOL DANS DES RESINES EPOXY LIQUIDES Download PDF

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Publication number
WO1995011266A1
WO1995011266A1 PCT/US1994/001502 US9401502W WO9511266A1 WO 1995011266 A1 WO1995011266 A1 WO 1995011266A1 US 9401502 W US9401502 W US 9401502W WO 9511266 A1 WO9511266 A1 WO 9511266A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
glycol
reaction
parts
weight percent
Prior art date
Application number
PCT/US1994/001502
Other languages
English (en)
Inventor
Thomas J. Hairston
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to CA002174427A priority Critical patent/CA2174427A1/fr
Priority to PL94314007A priority patent/PL174545B1/pl
Priority to BR9407843A priority patent/BR9407843A/pt
Priority to AU62980/94A priority patent/AU6298094A/en
Priority to EP94910685A priority patent/EP0724605A1/fr
Priority to KR1019960701984A priority patent/KR960704958A/ko
Priority to JP7511728A priority patent/JPH09503809A/ja
Publication of WO1995011266A1 publication Critical patent/WO1995011266A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • C08G59/1427—Polycondensates modified by chemical after-treatment with inorganic compounds with water, e.g. hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment

Definitions

  • Liquid epoxy resin is usually made by reacting a dihydric phenol, such as bisphenol
  • the resulting resin usually contains predominantly the diglycidyl ether of the dihydric phenol, with minor quantities of oligomer and or resin that is terminated by ⁇ -glycol groups.
  • the dihydric phenol and the diglycidyl ether are preferably represented by Formula 1 :
  • Ar represents an aromatic group.
  • Each Q is a hydroxyl group in the dihydric phenol, and Q is a glycidyl ether moiety represented by Formula (2) in the epoxy resin.
  • Each R represents a hydrogen atom, a halogen or a lower alkyl group.
  • n represents a number of repeating units, "n” is usually 0.1 to 0.2 in liquid epoxy resin.
  • ⁇ -glycol groups which are preferably represented by Formula (3):
  • the resin For many uses, it is desirable for the resin to contain only a very small amount of ⁇ -glycol.
  • resins that contain more than 2 percent ⁇ -glycol are difficult to wash after they are made because they form emulsions when impurities are washed from the resin using water.
  • resins that contain very low levels of ⁇ -glycol have superior performance properties for many applications, such as high glass-transition temperature in electrical laminates. Therefore, it is frequently desirable to manufacture liquid epoxy resin that contains very low levels of ⁇ - glycol. This can easily be done by removing hydrolysis products of epihalohydrin from recycled epihalohydrin before returning the epihalohydrin to the reaction vessel.
  • mono- ⁇ -glycol-containing resin in which one Q is a glycidyl ether moiety of Formula (2) and the other Q is an ⁇ -glycol of Formula (3)
  • mono- ⁇ -glycol resin greatly accelerate the curing of liquid epoxy resin with amine catalyst.
  • resins that contain moderate amounts of mono- ⁇ -glycol resin interact better with thixotropic agents and flow modifiers. Therefore, it is desirable to increase the levels of mono- ⁇ -glycol resin in liquid epoxy resins that contain very little ⁇ -glycol, for some uses.
  • bis- ⁇ -glycol resin in which both Q are ⁇ -glycol moieties of Formula (3)
  • the known processes have drawbacks which make them undesirable for use in mass producing large quantities of liquid epoxy resin that contain moderate ⁇ -glycol content.
  • What is needed is a process to moderately increase the level of mono- ⁇ -glycol resin in an epoxy resin to a desired level without the need for a catalyst or solvent.
  • the present invention is a process in which a mixture of liquid epoxy resin and water is reacted at elevated temperatures in order to hydrolyze epoxy groups into ⁇ -glycol groups, characterized in that:
  • the reaction temperature is between 130°C and 200°C; (2) the reaction mixture contains between 0.5 and 10 parts water per 100 parts resin by weight; and (3) the mixture contains 0 to 1 weight percent organic solvents and 0 to 100 ppm each of: organic acids, organic diacids, phosphonium compounds, and alkali or alkaline earth metals and their salts.
  • the parts and percentages are preferably measured by high performance liquid chromatography as described in Example 1.
  • the process has several advantages over the prior art. It can be run either in a batch fashion or continuously. It can easily make liquid epoxy resin that contains commercially desirable levels of mono- ⁇ -glycol resin. It makes little or no bis- ⁇ -glycol resin. It uses no catalyst, so only water needs to be separated at the completion of the reaction.
  • the resin can be used for ordinary thermoset uses, such as adhesives and coatings.
  • the present invention uses a liquid epoxy resin. Suitable resins and processes to make them are described previously.
  • the non-oligomerized resin contains an aromatic group (Ar) linking two glycidyl ether moieties (Q), as illustrated in Formula 1.
  • the aromatic group contains an aromatic ring or a moiety containing two fused or unfused aromatic rings.
  • the aromatic rings are preferably carbocyclic. They may have substituents that do not interfere with the manufacture or use of the resin, such as lower (C** to C ⁇ ) alkyl groups, halogen atoms or alkoxy groups, but they are preferably unsubstituted. Unfused rings may be linked by a bond or by a divalent moiety that does not interfere with the manufacture or use of the resin.
  • divalent moieties include an oxygen atom, a lower hydrocarbyl group, a halogenated lower hydrocarbyl group, a ketone group and a fluorene group.
  • the hydrocarbyl groups are preferably alkylene groups.
  • the divalent moiety is preferably a methylene or isopropylene moiety, and is most preferably isopropylene.
  • Each Ar is most preferably a 2,2-bis- (p-phenylene)-isopropylidene moiety, which optionally contains methyl or halogen substituents bonded to the phenylene rings.
  • Each R in Formulae 1 , 2, and 3 is preferably hydrogen.
  • the liquid epoxy resin usually contains small quantities of oligomer and ⁇ -glycol-containing resins at the commencement of the reaction.
  • the liquid epoxy resin preferably contains 70 to 100 weight percent diglycidyl ether of the dihydric phenol, more preferably 80 to 90 weight percent, and most preferably 85 weight percent.
  • the liquid epoxy resin preferably contains 0 to 30 weight percent oligomer, more preferably 10 to 20 weight percent oligomer, and most preferably 15 weight percent oligomer.
  • the oligomers are preferably represented by Formula 1 , wherein "n" is 0 or greater. The average "n" is preferably 0 to 0.2, more preferably 0.10 to 0.15 and most preferably 0.12.
  • the process can use resins that contain low, moderate or high levels of ⁇ -glycol, but it is most useful with resins that contain relatively little ⁇ -glycol.
  • the starting liquid epoxy resin preferably contains 0 to 2 weight percent ⁇ -glycol-containing species, more preferably 0 to 1 weight percent ⁇ -glycol-containing species, and most preferably 0 to 0.5 weight percent ⁇ -glycol-containing species.
  • the quantity of ⁇ -glycol in the resin is preferably no more than 1 equi alent percent of the quantity of glycidyl ether moieties, more preferably no more than 0.5 equivalent percent, and most preferably, no more than 0.3 equivalent percent. It is possible that the liquid epoxy resin may contain small quantities of impurities from previous steps.
  • the liquid epoxy resin preferably contains less than 100 ppm of those impurities, more preferably less than 50 ppm, more highly preferably less than 25 ppm and most preferably less than about 10 ppm.
  • the liquid epoxy resin preferably contains no more than 5 ppm sodium, 6 ppm inorganic chloride and 10 ppm epichlorohydrin.
  • the liquid epoxy resin contains 0 ppm of those impurities.
  • impurities such as common organic solvents
  • common solvents include aromatic and polar organic solvents that are liquid at 25°C, such as toluene, xyiene, alkyl ketones, glycols, ethers and glycol ethers and alcohols.
  • the liquid epoxy resin preferably contains no more than about 1 weight percent of those impurities, more preferably no more than 0.5 weight percent and most preferably no more than 0.1 weight percent.
  • Preferred resins are commercially available from The Dow Chemical Company under the trademark D.E.R.TM 330 and D.E.R.TM 383 (trademark of The Dow Chemical Company). They can also be made by the processes described previously.
  • the reaction temperature is preferably at least 145°C and more preferably at least 165°C.
  • the reaction temperature is preferably no more than 180°C and more preferably no more than 175°C.
  • the resin is contacted with water either before, du ring or after it has been heated.
  • the resin is preferably heated to reaction temperature before it is contacted with the water. It is not critical whether the water is added to the reaction vessel as liquid water or as steam.
  • the water is preferably added as steam.
  • the ratio of water to resin is preferably at least 0.5 phr water, more preferably at least 1 phr water and most preferably at least 2 phr water.
  • the ratio of water to epoxy resin is preferably no more than 8 phr, and more preferably no more than 5 phr.
  • the pressure of the reaction is not critical as long as the reagents remain in contact with each other.
  • the pressure is preferably at least about the vapor pressure of water at the reaction temperature, in order to keep water in the reaction mixture.
  • the pressure is preferably at least 24 psig (260 kPa) and more preferably at least 85 psig (680 kPa).
  • the pressure is preferably no more than 1000 psig (7 MPa), and more preferably no more than 250 psig (1.8 MPa).
  • the atmosphere is not critical, as long as it does not substantially interfere with the reaction.
  • reaction time is not critical as long as the reaction is allowed to proceed until the desired level of ⁇ -glycol is produced.
  • the optimum time may vary depending upon the reaction conditions, the quantity of ⁇ -glycol in the starting liquid epoxy resin, and the desired quantity in the finished product.
  • the reaction or residence time is at least 0.5 hours, more preferably at least 1 hour, and most preferably at least 2 hours; the reaction or residence time is preferably no more than 8 hours, more preferably no more than 6 hours, and most preferably no more than 4 hours.
  • the reaction is preferably not run beyond 8 hours, in order to limit formation of bis- ⁇ -glycol resin.
  • the reaction is run essentially without hydrolysis catalysts or solvents. This means that significant quantities of catalyst and solvent should not be added to the reaction mixture intentionally.
  • Hydrolysis catalysts that should not be added include organic acids and diacids, phosphonium compounds, and alkali or alkaline earth metals or their salts.
  • Common solvents that should not be added include aromatic and polar organic solvents, as previously described. Acceptable quantities of these impurities are described previously.
  • unreacted water is preferably removed by ordinary techniques, such as by flash distillation and/or by air-drying or stripping. Flash distillation preferably occurs at about reaction temperatures under atmospheric or subatmospheric pressures. Thereafter, the resin is preferably cooled to less than 80°C before it is stored.
  • the finished resin preferably contains at least 1 weight percent mono- ⁇ -glycol species, more preferably at least 2 weight percent mono- ⁇ -glycol species, and most preferably at least 4 weight percent mono- ⁇ -glycol species. It preferably contained no more than 8 weight percent mono- ⁇ -glycol species, more preferably no more than 7 weight percent mono- ⁇ -glycol species and most preferably no more than 6 weight percent mono- ⁇ -glycol species.
  • the ratio of ⁇ -glycol moieties to glycidyl ether moieties is preferably at least 0.5 equivalent percent, more preferably at least 1 equivalent percent and most preferably at least 2 equivalent percent. The ratio is preferably no more than 4 equivalent percent, more preferably no more than 3.5 equivalent percent and most preferably no more than 3 equivalent percent.
  • the reaction preferably increases the quantity of mono- ⁇ -glycol species in the resin by at least 1 weight percent, more preferably at least 2 weight percent and most preferably at least 4 weight percent. It preferably increases the quantity of mono- ⁇ -glycol species in the liquid epoxy resin by no more than 8 weight percent, and more preferably no more than 6 weight percent.
  • the reaction preferably increases the ratio of ⁇ -glycol to glycidyl ether moieties in the resin by at least 0.5 equivalent percent, more preferably at least 1 equivalent percent and most preferably at least 2 equivalent percent. It preferably increases the ratio of ⁇ -glycol to glycidyl ether moieties in the resin by no more than 4 equivalent percent, and more preferably no more than 3 equivalent percent.
  • the finished resin preferably contains no more than 1 weight percent bis- ⁇ -glycol resin, more preferably no more than 0.5 weight percent, and most preferably no more than 0.1 weight percent.
  • the finished resin can be used for any ordinary purpose that epoxy resins are used, such as adhesives, coatings, and matrix resins in matrix composites.
  • Working Examples The following examples are for illustrative purposes only, and are not intended to limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
  • a 2 L agitated pressure reactor was charged with 1000 g of liquid epoxy resin containing 80.28 percent diglycidyl ether of bisphenol A and 0.4 percent mono- ⁇ -glycol of the diglycidyl ether of bisphenol A. The remainder of the liquid epoxy resin was oligomers of the diglycidyl ether of bisphenol A (except for trace impurities).
  • the reactor was purged with nitrogen to exclude air and heated to 180°C. 50 g of deionized water was added to the reactor, taking care to avoid the introduction of air.
  • the reactor was cooled to 172°C and the reaction was continued at 172°C with agitation for 30 minutes.
  • Example 2 The process of Example 1 was repeated, except that the reactor was cooled to
  • Example 3 The reaction in Example 1 was repeated except that the reaction temperature was
  • Example 3 The reaction of Example 3 was repeated. The analyzed sample was found to contain 74.78 weight percent diglycidyl ether of bisphenol A and 4.88 weight percent mono- ⁇ - glycol of the diglycidyl ether of bisphenol A.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Les performances de résines époxy dans différentes utilisations finales sont accrues grâce à la présence de petites quantités de résine hydrolysée terminée par des groupes α-glycol. Cette invention concerne un procédé dans lequel un mélange qui contient une résine époxy liquide et de l'eau est amené à réagir à des températures élevées afin de convertir par hydrolyse les groupes époxy en groupes α-glycol, ce procédé se caractérisant en ce que: (1) la température de réaction est comprise entre 130 °C et 200 °C; (2) le mélange de réaction contient 0,5 à 10 parties d'eau pour 100 parties de résine en poids; et (3) ledit mélange contient 0 à 1 pour cent en poids de solvants organiques et 0 à 100 ppm chacun de: acides organiques, diacides organiques, composés de phosphonium et métaux alcalins ou alcalino-terreux et leurs sels. Ce procédé permet d'augmenter le niveau des groupes α-glycol dans la résine mais sans utiliser de solvants ni de catalyseurs, de sorte qu'il est facile de nettoyer la résine qui en résulte.
PCT/US1994/001502 1993-10-18 1994-02-14 PROCEDE POUR AUGMENTER LE NIVEAU DE α-GLYCOL DANS DES RESINES EPOXY LIQUIDES WO1995011266A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA002174427A CA2174427A1 (fr) 1993-10-18 1994-02-14 Procede pour augmenter le niveau de .alpha.-glycol dans des resines epoxy liquides
PL94314007A PL174545B1 (pl) 1993-10-18 1994-02-14 Sposób zwiększania poziomu alfa-glikolu w ciekłej żywicy epoksydowej
BR9407843A BR9407843A (pt) 1993-10-18 1994-02-14 Processo para hidrolisar grupos epoxi a grupos &-glicol
AU62980/94A AU6298094A (en) 1993-10-18 1994-02-14 Method to increase the level of alpha-glycol in liquid epoxy resin
EP94910685A EP0724605A1 (fr) 1993-10-18 1994-02-14 PROCEDE POUR AUGMENTER LE NIVEAU DE $g(a)-GLYCOL DANS DES RESINES EPOXY LIQUIDES
KR1019960701984A KR960704958A (ko) 1993-10-18 1994-02-14 액체 에폭시 수지 중의 α-글리콜의 수준을 증가시키는 방법(Method to increase the level of α-glycol in liquid epoxy resin)
JP7511728A JPH09503809A (ja) 1993-10-18 1994-02-14 液体エポキシ樹脂中のα−グリコール含有分を上げる方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/138,661 1993-10-18
US08/138,661 USH1439H (en) 1993-10-18 1993-10-18 Method to increase the level of α-glycol in liquid epoxy resin

Publications (1)

Publication Number Publication Date
WO1995011266A1 true WO1995011266A1 (fr) 1995-04-27

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PCT/US1994/001502 WO1995011266A1 (fr) 1993-10-18 1994-02-14 PROCEDE POUR AUGMENTER LE NIVEAU DE α-GLYCOL DANS DES RESINES EPOXY LIQUIDES

Country Status (10)

Country Link
US (1) USH1439H (fr)
EP (1) EP0724605A1 (fr)
JP (1) JPH09503809A (fr)
KR (1) KR960704958A (fr)
AU (1) AU6298094A (fr)
BR (1) BR9407843A (fr)
CA (1) CA2174427A1 (fr)
PL (1) PL174545B1 (fr)
TW (1) TW293828B (fr)
WO (1) WO1995011266A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2726531B1 (fr) 2011-06-30 2015-07-22 Dow Global Technologies LLC Composition de résine époxyde durcissable contenant des mixtures des durcisseurs aminiques et un excès des groups epoxides
WO2015148039A1 (fr) 2014-03-24 2015-10-01 Dow Global Technologies Llc Compositions de résine époxyde partiellement hydrolysée
US11045421B2 (en) 2013-08-07 2021-06-29 Incyte Corporation Sustained release dosage forms for a JAK1 inhibitor
US11214573B2 (en) 2011-06-20 2022-01-04 Incyte Holdings Corporation Azetidinyl phenyl, pyridyl or pyrazinyl carboxamide derivatives as JAK inhibitors
US11285140B2 (en) 2010-03-10 2022-03-29 Incyte Corporation Piperidin-4-yl azetidine derivatives as JAK1 inhibitors
US11331320B2 (en) 2005-12-13 2022-05-17 Incyte Holdings Corporation Heteroaryl substituted pyrrolo[2,3-b]pyridines and pyrrolo[2,3-b]pyrimidines as Janus kinase inhibitors
US11337927B2 (en) 2012-11-15 2022-05-24 Incyte Holdings Corporation Sustained-release dosage forms of ruxolitinib
US11833155B2 (en) 2020-06-03 2023-12-05 Incyte Corporation Combination therapy for treatment of myeloproliferative neoplasms

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8053031B2 (en) * 2007-07-26 2011-11-08 Raven Lining Systems Inc. Two-part epoxy composition
SG188261A1 (en) * 2010-09-02 2013-04-30 Sumitomo Bakelite Co Fixing resin composition for use in rotor
US8693224B1 (en) 2012-11-26 2014-04-08 Arctic Sand Technologies Inc. Pump capacitor configuration for switched capacitor circuits
JP6512392B2 (ja) * 2013-05-29 2019-05-15 ナガセケムテックス株式会社 エポキシ化合物、エポキシ組成物及び接着剤

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3405093A (en) * 1966-12-05 1968-10-08 Dow Chemical Co Process for hydrolyzing polyepoxide resins
US4072638A (en) * 1972-05-15 1978-02-07 Solvay & Cie Halogenated polyether polyols and polyurethane foams produced therefrom
US4324822A (en) * 1979-07-06 1982-04-13 Toyo Seikan Kaisha Ltd. Metal can paint providing coating retaining high adhesion even with lapse of time
US4404335A (en) * 1982-08-16 1983-09-13 The Dow Chemical Company Hydrolyzing epoxy resins in absence of solvent and in presence of oxalic acid and a phosphonium compound

Family Cites Families (1)

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US4358577A (en) * 1980-11-26 1982-11-09 The Dow Chemical Company Method for preparing high molecular weight epoxy resins containing hydrolyzed epoxy groups

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3405093A (en) * 1966-12-05 1968-10-08 Dow Chemical Co Process for hydrolyzing polyepoxide resins
US4072638A (en) * 1972-05-15 1978-02-07 Solvay & Cie Halogenated polyether polyols and polyurethane foams produced therefrom
US4324822A (en) * 1979-07-06 1982-04-13 Toyo Seikan Kaisha Ltd. Metal can paint providing coating retaining high adhesion even with lapse of time
US4404335A (en) * 1982-08-16 1983-09-13 The Dow Chemical Company Hydrolyzing epoxy resins in absence of solvent and in presence of oxalic acid and a phosphonium compound

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 113, no. 2, 9 July 1990, Columbus, Ohio, US; abstract no. 8047t, P.S. SHEIH: "Fundamental studies of epoxy resins for can and coil coatings" page 91; *
J. COAT. TECHNOL., vol. 62, 1990, pages 25-30 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11331320B2 (en) 2005-12-13 2022-05-17 Incyte Holdings Corporation Heteroaryl substituted pyrrolo[2,3-b]pyridines and pyrrolo[2,3-b]pyrimidines as Janus kinase inhibitors
US11744832B2 (en) 2005-12-13 2023-09-05 Incyte Corporation Heteroaryl substituted pyrrolo[2,3-b]pyridines and pyrrolo[2,3-b]pyrimidines as Janus kinase inhibitors
US11285140B2 (en) 2010-03-10 2022-03-29 Incyte Corporation Piperidin-4-yl azetidine derivatives as JAK1 inhibitors
US11214573B2 (en) 2011-06-20 2022-01-04 Incyte Holdings Corporation Azetidinyl phenyl, pyridyl or pyrazinyl carboxamide derivatives as JAK inhibitors
EP2726531B1 (fr) 2011-06-30 2015-07-22 Dow Global Technologies LLC Composition de résine époxyde durcissable contenant des mixtures des durcisseurs aminiques et un excès des groups epoxides
US11337927B2 (en) 2012-11-15 2022-05-24 Incyte Holdings Corporation Sustained-release dosage forms of ruxolitinib
US11576864B2 (en) 2012-11-15 2023-02-14 Incyte Corporation Sustained-release dosage forms of ruxolitinib
US11576865B2 (en) 2012-11-15 2023-02-14 Incyte Corporation Sustained-release dosage forms of ruxolitinib
US11896717B2 (en) 2012-11-15 2024-02-13 Incyte Holdings Corporation Sustained-release dosage forms of ruxolitinib
US11045421B2 (en) 2013-08-07 2021-06-29 Incyte Corporation Sustained release dosage forms for a JAK1 inhibitor
WO2015148039A1 (fr) 2014-03-24 2015-10-01 Dow Global Technologies Llc Compositions de résine époxyde partiellement hydrolysée
US11833155B2 (en) 2020-06-03 2023-12-05 Incyte Corporation Combination therapy for treatment of myeloproliferative neoplasms

Also Published As

Publication number Publication date
EP0724605A1 (fr) 1996-08-07
USH1439H (en) 1995-05-02
PL314007A1 (en) 1996-08-05
BR9407843A (pt) 1997-05-13
PL174545B1 (pl) 1998-08-31
AU6298094A (en) 1995-05-08
JPH09503809A (ja) 1997-04-15
TW293828B (fr) 1996-12-21
CA2174427A1 (fr) 1995-04-27
KR960704958A (ko) 1996-10-09

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