Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-08-02
2004-08-10
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S547000, C568S609000, C568S619000, C568S648000
Reexamination Certificate
active
06774250
ABSTRACT:
The present invention relates to the preparation of liquid reaction products of cycloaliphatic epoxides with multifunctional hydroxy compounds, the use of the product as obtained by the process for preparing a curable composition, the curable composition and its use.
The reaction between alcohols and cycloaliphatic epoxides in the presence of an heterogeneous catalyst is known. For example G. H. Posner et al., describe in
Tetrahedron Letters
No. 42, 3597-3600, 1975 the reaction of alcohols with cyclohexene oxide using W-200 alumina to form the corresponding trans-2-alkoxycyclohexanols in good yields. This process uses an excess of the alcohol wherein only monofunctional materials are used.
The reaction of low molecular weight glycidyl epoxy materials with polyhydric compounds in the presence of a homogeneous catalyst is known. This process converts low molecular weight glycidyl epoxy materials of high epoxide content into higher molecular weight material of reduced epoxide content.
For example, U.S. Pat. No. 4,543,430, discloses a process for the preparation of addition products of epoxides and hydroxylated compounds, the epoxide being an alkylene oxide or epichlorhydrin, and the hydroxylated compound being an alcohol, an alkyleneglycol monoalkyl ether, a pheriol or water. The ratio of the hydroxylated compound to the epoxide ranges from 2 to 20 percent by weight. The reaction is carried out in a homogeneous liquid phase at a temperature between 40° and 250° C. in the presence of a catalyst. The catalyst is a) a tetraalkylammonium triflate (trifluormethanesulphonate) or b) a triflic acid (trifluormethanesulphonic acid) salt of a metal selected from an alkali metal salt, an alkali earth metal salt, aluminum, cobalt, nickel, zirconium and tin. The amount of catalyst used is such that the catalyst concentration in the reaction mixture ranges from 1 to 100 ppm by weight it is stated at col. 1, lines 15 to 17, that the product preferably being sought is generally an addition product comprising a single unit derived from the epoxide, per molecule. Such products will be of low molecular weight.
U.S. Pat. No. 5,362,835 discloses the addition reaction of an epoxide with a dihydroxy compound in the presence of a triflate salt of a metal of Group IIA, IIB, IIIA, IIIB or VIIIA of the Periodic Table of Elements. The drawback of this process is seen in the fact that the triflate salt catalyst has to be deactivated in a separate reaction step.
It has now been found that the use of surface-active heterogeneous catalysts avoids the deactivation and loss of the homogeneous catalyst.
The present invention relates to the advancement of polycycloaliphatic epoxides with multifunctional alcohols, which produces, under controlled conditions in the presence of surface-active heterogeneous catalysts, materials having increased molecular weights and terminated by cycloaliphatic epoxy groups. The resulting advanced epoxides are liquid with measurable epoxide content greater than 0.1 mol/kg. In a preferred embodiment, the advanced epoxides have an epoxide content greater than 1.5 mol/kg, in particular greater than 2.0 mol/kg.
Subject matter of the present invention is a process for the preparation of reaction products of cycloaliphatic epoxides with mono- or multifunctional hydroxy compounds which comprises reacting a polyfunctional cycloaliphatic epoxy resin with a mono- or a multifunctional hydroxy compound in the presence of a heterogeneous surface-active catalyst selected from the group consisting of activated aluminum hydroxide, hydrated aluminum oxide, amorphous silica, activated carbon and cationic ion exchange resins and isolating the reaction product.
The polyfunctional epoxy resins of this invention are cycloaliphatic and contain the epoxy group of the formula:
wherein R is a straight chain C
2
-C
6
alkylene group, especially C
4
-alkylene which may be substituted by additional substituents, such as C
1
-C
4
alkyl. These epoxy resins may be formed by reaction of peracetic acid with olefinic esters of cycloaliphatic compounds. Some preferred cycloaliphatic epoxy resins are diepoxides and include but are not limited by the following:
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
bis(2,3-epoxycyclopentyl)ether,
bis(3,4-epoxycyclohexyl methyl)adipate, and
2-(3,4-epoxycyclohexyl-5,5-spiro)-(3,4-epoxy)cyclohexane-m-dioxane. Diepoxides containing non-terminal epoxide groups may also be employed, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene oxide, 4-oxatetracyclo[6,2,1,0
2,7
0
3,5
]undec-9-yl glycidyl ether, bis(4-oxatetracyclo[6,2,1,0
2,7
0
3,5
]undec-9-yl)ether of ethylene glycol, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and its 6,6
1
-dimethyl derivative, bis(3,4-epoxycyclohexanecarboxylate) of ethylene glycol and 3-(3,4-epoxycyclohexyl)-8,9-epoxy-2,4 dioxaspiro[5,5]undecane.
In a preferred embodiment of the process the polyfunctional cycloaliphatic epoxy resin is selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bis (3,4-epoxycyclohexyl methyl) adipate carboxylate.
The mono- or multifunctional hydroxyl compounds used according to the process of the present invention may contain primary, secondary or tertiary alcohols.
Preferred hydroxyl compounds are those having the formula:
Q(OH)
n
(II)
in which Q is an aliphatic, cycloaliphatic or araliphatic residue and n are integers from 1 up to 128. When Q is an aliphatic residue, it may be a straight or branched chain C
2
-C
12
alkylene residue.
Cycloaliphatic residues 0 are preferably C
5
-C
8
cycloalkylene residues in which the cycloalkylene group may be substituted by substituents such as C
1
-C
4
alkyl or several cycloalkylene residues may be bonded together via a bridge member, e.g. a methylene bridge.
Araliphatic residues are preferably optionally ring-substituted benzyl residues or naphthyl methylene residues.
Each of the residues Q may be substituted or interrupted provided that the substituent groups or interrupting atoms do not deactivate the heterogeneous catalyst, or undergo competing reactions with the liquid epoxy. Examples of suitable substituent groups are ester groups as contained in polycaprolactones and unsaturated groups as contained in hydroxy-terminated polybutadienes or polybutadiene polymers.
The alcohols mentioned above may be substituted by alkoxy groups as well as higher polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and polycaprolactone groups based on such alcohols.
Specific examples of preferred aliphatic hydroxy compound reactants of formula II (where n=1) include methanol, ethanol, propanol, butanol and such straight chain or branched alcohols up to and including C
12
alkanols.
Specific examples of cycloaliphatic alcohols include cyclopentanol, cyclohexanol and cycloheptanol as well as such alcohols substituted by C
1
-C
4
alkyl and/or alkoxy groups.
Araliphatic alcohols which may be mentioned include benzyl alcohol and phenoxy ethanol which both may have ring substitution such as C
1
-C
4
alkyl and/or alkoxy groups, halogens such as F, Cl, Br, I or other groups provided that the substituent groups do not deactivate the heterogeneous catalyst, or undergo competing reactions with the liquid epoxy.
Specific examples of preferred aliphatic dihydroxy compounds reactants of formula II (where n=2) include ethylene glycol, diethylene glycol, triethylene glycol and higher polyoxyethylene glycols; propane-1,2-diol; propane-1,3-diol and higher propoxylene glycols; butane-1,4-diol and higher polyoxytetramethylene glycols; polycaprolactone diols; neopentyl glycol; pentane-1,5-diol; hexane-1,6-diol and octane-1,8-diol.
Specific examples of preferred cycloaliphatic diols are e.g. quinitol, resorcitol, bis (4-hydroxycyclohexyl) methane, 2,2-bis(4-hydroxycyclohexyl) propane, cyclohexane dimethanol and 1,1-bis(hydroxymethyl)cyclohex-3-ene and 4,9-bis(hydroxymethyl)tricyclo[5,2,1,0
2,6
]decane.
Araliphatic dial reactants which may be menti
Barker Pauline G.
Hatton Kevin B.
Rabener Christiane
Rabener Claus W.
Huntsman Advanced Materials Americas Inc.
Levato Tiffany A.
Neuman Kristin H.
Proskauer Rose LLP
Trinh Ba K.
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