Process for the manufacture of epoxy compounds

Details Process for the manufacture of epoxy compounds Process for the manufacture of epoxy compounds

1998-08-13

2001-01-09

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From heterocyclic reactant containing as ring atoms oxygen,...

C528S307000, C528S360000, C528S364000, C528S419000

Reexamination Certificate

active

06172182

ABSTRACT:

The invention is relating to a process for the manufacture of epoxy compounds. More in particular the invention is relating to a process for the manufacture of epoxy compounds without the involvement of halogen and in particular chlorine gas.
Epoxy compounds, which are manufactured in a great variety on large industrial scales throughout the world, are used for an extensive scale of end applications, such as the manufacturing of shaped articles, including embedded small electronic components such as semi-conductors or chips and the prepregs for the subsequent manufacture of printed circuits for the electronic industry, coatings including the organic solvent based coatings as well as the more modern aqueous epoxy resin dispersion coatings, and in particular can and drum coatings, composites and laminates showing great flexibility, and the like.
Said starting epoxy compounds were manufactured up to now by means of the starting reagent epihalohydrin and in particular epichlorohydrin, which in its turn was manufactured via allylchloride, prepared from propene and gaseous chlorine.
It will be appreciated that on the one hand, there has been developed in the last decade and in particular in the last five years, an increasing pressure from national or regional governmental regulations and requirements to chemical process industry, in order to drastically reduce possible chlorine emissions or even to avoid the use of chlorine completely, and on the other hand, in the current manufacturing processes for chlorination of propene in the gaseous phase there is still a need to improve the relatively low yield and to diminish the high fouling tendency.
Moreover, during the reaction of epihalohydrin with phenolic compounds to form epoxy resin it is not possible to avoid completely that halogen, originating from the epihalohydrin, is intermingled in a resin as a product in the form that the halogen atom is chemically bound to the epoxy resin itself.
As one of the important applications of the epoxy resin is encapsulation of micro electronic material, it will be appreciated that this intermingled halogen liberates as an acid by moisture, during use of the final article for a long period of time and this acid leads to corrosion of a metal material.
Therefore one object of the present invention is formed by a process, meeting the requirements of the application conditions and of the present environmental legislation and that one presumably enforced in the near future, and starting from cheap and generally available basic chemicals.
One of the alternative manufacturing routes for epoxy resins, proposed in the past was that according the following simplified reaction scheme:
wherein R
1
represents a residue comprising one or more additional phenol groups, wherein R
2
represents a residue comprising one or more additional groups of the formula.
wherein R
3
represents a residue comprising one or more additional groups of the formula:
and wherein R
4
represents a residue comprising one or more additional groups
Although it was already known from e.g. Japanese patent application Sho 61-33180 A, to produce epoxy compounds by decarboxylating a carbonate compound, using as catalyst a combination of an alkali metal halide and of a dihydrogenphosphate of an alkali metal while earlier proposed similar processes were known from e.g. JP-Sho-57-77682 A and U.S. Pat. No. 2,856,413, said route could not be used for economical manufacture of epoxy compounds up to now.
In particular from JP-Sho-61-33180 it will be appreciated that the finally obtained mono-epoxy compounds had such a simple molecular structure, that they could be recovered from the initially crude reaction mixture by distillation.
However such a distillation has appeared to be not possible for the commercial standard difunctional and multifunctional epoxy compounds aimed at.
Therefore there was still a strong need for improvement of this proposed route to enable industrial scale manufacture at all.
As a result of extensive research and experimentation it has now been surprisingly found, that compounds of the formula
wherein Ra represents
(1) a group
wherein Rp represents hydrogen
or a residue, comprising one or more additional groups of the formula
(2) a group Rq&Parenopenst;Q&Parenclosest;
b
-alkyl&Parenopenst;Q&Parenclosest;
a
- wherein the alkyl group is straight or branched and contains from 2 to 30 carbon atoms wherein Q is aryl of from 6 to 20 carbon atoms (preferably phenyl) or cycloalkyl from 6 to 20 carbon atoms (preferably cyclohexyl) and a and b are 0 or 1, wherein Rq represents hydrogen or a residue, comprising one or more additional groups of the formula
(3) a group
wherein Rs represents hydrogen or a residue comprising one or more additional groups of the formula
(4) a group
wherein Rt represents hydrogen or a residue comprising one or more additional groups of the formula:
wherein Rx and Ry may represent hydrogen or only one of the symbols Rx and Ry may represent alkyl, having from 1 to 4 carbon atoms (preferably methyl), wherein n is an integer from 1 to 100 and preferably from 5 to 50,
can be very efficiently reacted with alkylene oxide having from 1 to 20 carbon atoms (preferably from 1 to 4 carbon atoms), in the presence of a catalyst, selected from the group of compounds containing at least one cation:
wherein A represents nitrogen or phosphorus and preferably phosphorus, wherein R
c
, R
d
and R
e
each represent an optionally substituted alkyl group having 1 to 10 carbon atoms and preferably from 1 to 4, or an optionally substituted phenyl group and wherein R
g
represents an alkyl group having from 1 to 6 carbon atoms which may optionally be terminally substituted by an aryl group (preferably phenyl) or by a group of formula,
in combination with a counter anion X
−
selected from halogen, acetate, phosphate or carboxylate or combinations thereof, to form alkylene carbonate or alkylene sulfite and a compound
wherein Rb represents
(1) a group
wherein Rf represents hydrogen or a residue comprising one or more additional groups of the formula
(2) a group Rj&Parenopenst;Q&Parenclosest;
b
-alkyl&Parenopenst;Q&Parenclosest;
a
-, wherein the alkyl group is straight or branched and contains from 2 to 30 carbon atoms, wherein Q is aryl of from 6 to 20 carbon atoms (preferably phenyl) or cycloalkyl from 6 to 20 carbon atoms (preferably cyclohexyl) and a and b are 0 or 1,
wherein Rj represents hydrogen or a residue comprising one or more additional groups of the formula:
(3) a group
wherein Rh represents hydrogen or a residue comprising one or more additional groups of the formula
(4) a group
wherein Rx and Ry are as defined hereinbefore and Ri represents hydrogen or a residue comprising one or more additional groups of the formula
According to a preferred embodiment of this process step, the counter anion is selected from halogen and more preferably this counter anion is chlorine.
The substituents of the alkyl groups or phenyl groups R
c
, R
d
and R
e
may be selected from halogen, nitro, alkyl or alkoxy having from 1 to 4 carbon atoms, carboxyl or sulphonic acid groups. More preferably the alkyl or phenyl groups R
c
, R
d
and R
e
are unsubstituted or the phenyl groups are monosubstituted on the ortho place.


REFERENCES:
patent: 2856413 (1958-10-01), Malkemus et al.
patent: 4276223 (1981-06-01), Wu
patent: 4390732 (1983-06-01), Merk et al.
patent: 46455 (1966-03-01), None
patent: 1940205 (1969-08-01), None
patent: 4213010 (1993-10-01), None
patent: 47473 (1981-09-01), None
patent: 57-077682 (1982-05-01), None
patent: 61-033180 (1986-02-01), None
Patent Abstracts of Japan vol. 010, No. 136 (C-347) May 20, 1986 & JP 60 260568 A (Daicel Kagaku Kogyo KK), Dec. 23, 1985, see abstract.

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