Note: Descriptions are shown in the official language in which they were submitted.
~L~775~3
The presen-t invention rela-tes to a process for the
manufacture of polycarboxylic acid polyglycidyl esters by
transesterification of polycarboxylic acid polyalkyl esters
wi-th glycidol.
Several processes for -the manufacture of polycar-
boxylic acid polyglycidyl esters are already known. Of the
four methods described in a summary in the introduc-tion to
"Die Angewandte Makromolekulare Chemie 31, (1973), 83-113",
namely
a) the reaction of glycidol with acid chlorides,
b) the reaction of epichlorohydrin with salts of acids,
c) the reaction of epichlorohydrin wi-th acids and subsequen-t
dehyclrohalogenation, and
d) the epoxida-tion of allyl esters~
only the reaction of epichlorohydrin with carboxylic acids
with elimination of hydrogen chloride in the presence of
sodium hydroxide solution has been able to find accept~nce in
industry, so that dicarboxylic acid diglyG~yl esters to date
are obtained on an industrial scale almost exclusively by this
process However~ the products obtained according to this
process have the disadvantage that they cannot be manu~ac-tured
in a form ~ree from aliphatically bonded chlorine, that is to
say hydrolysable chlorine, and thus, because of the poorer
electrical properties of the resin and the corrosion-promo-ting
action of the chlorine, are not very sui-table ~or some
applications, especially for potting or encasing electrical
or electronic components. The method mentioned under d~
- 2 -
. .
~197~3
:~ .
that is to say -the epoxidation of allyl esters, is rarely
used for the rnanufacture of glycidyl esters because this
reaction is technologically difficult.
British Paten-t 1~118,206 already describes the manu-
facture of epoxide-esters by transesterifica-tion of mono-
carboxylic or dicarboxylic acid esters, for example of
dimethyl -terephthalate (Example 6) 9 with epoxide-alcohols in
the presence of alkaline catalysts. Glycidol is also
mentioned in general as an epoxide-alcohol suitable for this
purpose, but no corresponding illustrative example is given.
However, our own experiments have shown that the trans~
esterification of, for example, dimethyl terephthala-te with
glycidol in the presence of alkaline catalysts cannot be
carried out since, in addition to large amounts of a polymeric
solid product, only a reaction mixture which consists o~
about equal par-ts of diglycidyl terephthalate and glycidyl
methyl terephthalate and has a low epoxide content is obtained.
Furthermore, the manufac-ture of glycidyl methacrylate
by transesterification of methyl methacrylate with glycidol
in a less than e~uivalent amount and in the presence of
~hallium oxide as the ca-talyst is described in Example 8 of
French Patent 2,088,971, the me-thanol formed during the trans-
es-terification being distilled off azeotropically with the
methyl methacrylate present in excess. Based on the
glycidol employed, the yield of glycidyl methacrylate is only
65% of the theoretically obtainable amount and this is under-
standable when the tendency of glycidol to polymerise is taken r
`` ~Lal~75~3
into accoun-t. For the transes-terifi.ca-tion of dicarboxylic
~; acid dialkyl es-ters with glycidol -to give dicarboxylic acid
diglycidyl esters it was there~ore to be expected from the
start, because of the difunctionali-ty of the ester component,
that difficulties would be increased and, therefore, that
yields would be considerably less than 65%
It has now been found -that the transesterification of
polycarboxylic acid polyalkyl esters, especially dicarboxylic
acid dialkyl esters, with glycidol to give the corresponding
carboxylic acid polyglycidyl esters surprisingly can be
achieved with high yields and high epoxide content when -the
transesteri~ication is carried out wi-th at least stoichio-
metric amoun-ts o~ glycidol, preferably with a stoichiometric
excess of glycidol, and in the presence of thallium compounds
as the transesterification catalyst and preferably in an
organic solvent, and -the alcohol formed during the trans-
esteri~ication is removed continuously from the reaction mix-
ture and the transesterification temperature is so set that
the glycidol is not removed from -the reaction mixture during
the -transesterification reaction
The subjec-t of the present invention is thus a process
~or the manufacture of polycarboxylic acid polyglycidyl esters
of the formula I
A-~-C---O--CH2 C ---C~l~ (I)
wherein A denotes a single bond or, preferably, a n-valent
. -
~ 4 --
.; :
,. ~ ~ ~ ., , , .... , .,, .... .. , .; ,- .
~ )775Q3
aromatic, araliphatic, aliphatic, cycloaliphatic, heterocyclic, heterocyclic-
~ aliphatic or heterocyclic-aromatic radical and n represents the number 2, 3 or
: 4, characterized in that polycarboxylic acid polyalkyl esters of the formula II
A ~ COOR)n (II)
wherein R denotes an alkyl radical which contains 1 to 4 C atoms, are trans
esteri~ied with a~ least stoichiometric amounts of glycidol, in the presence
of a thallium co~pound as the catalyst, in a temperature range of 50 to 120C
and the alcohol formed during the ~ransesteTification is removed continuously
from the reaction mixture.
In particular, the invention relates to a process for the manufacture
of dicarboxylic acid diglycidyl esters of the ~ormula Ia
; O
C \ /H CH2 0 - C - A - C O - CH2 C\ - CH2 ~Ia)
wherein A denotes a divalent aromatic, araliphatic, aliphatic, cycloaliphatic,
heterocyclic, heterocyclic-aliphatic or heterocyclic-aromatic radical, character-
ized in that dicarboxylic acid dialkyl esters o the formula Ila
ROOC - A COOR~ ~IIa)
. .
,~
--5--
~.0775~3
wherein R and R' each denote an alkyl radical con-taining 1 -to
4 C atoms, are transesterified with at leas-t s-toichiometric
amounts oX glycidol, in the presence of a thallium compound
as the catalyst, in a -temperature range of 50 to 120C and
the alcohol formed during the transesterification is removecl
continuously from the reaction mix-ture.
Preferably, the process according to the invention
relates to the manufacture of dicarbox~Tlic acid diglycidyl
esters of the formula Ia, wherein A represents an aromatîc or
aliphatic radical, and is characterised in -that dicarboxylic
acid dialkyl esters o~ the formula IIa, wherein R and Rl each
denote an alkyl radical with 1 to 4 C atoms, are trans-
esterified with 1.05 to 1.5 mols of glycidol per 1 equivalent
of alkyl ester group, in the presence of thallium oxide, a
thallium salt, a thallium complex or an organo-thallium
compound, in an organic solvent in a temperature range of 60
to 90C.
In a particular embodiment of the process according
to the invention, the dimethyl esters or diethyl esters of
aromatic dicarboxylic acids are used as -the starting material.
Since the transesterification is always accompanied
by a more or less pronounced polymerisation of the epoxide
compounds, the transesterification should -take place as
rapidly as possible and under mild reaction conditions In
addi-tion to selecting the most advantageous catalyst and to
maintaining the optimum reaction temperature, it is important
to employ glycidol in a stoichiometric excess and continuously
- 6 -
~ . . ..
" :
~7~503
to remove from the reaction mix-ture only the alcohol which is
formed during -the transesteri~ication
In the process according to the invention, the stoi-
chiome-tric excess of glycidol can also pe more than 1.5 mols
o~ glycidol per 1 equivalent of alkyl--ester group but no
significant advantages are achieved by this.
The transesterification reaction is preferably
carried out in an organic solvent in which the reactants are
at leas-t partially soluble. When liquid polycarboxylic acid
polyalkyl esters or solid polycarboxylic acid polyalkyl
esters which are soluble or partially soluble in glycidol are
used, the transesterifica-tion reaction can also be carried out
without the addition of a solvent. Suitable organic sol-
~en-ts are those which have a boiling point which lies between
that of the alcohol formed during the transesterification and
that of glycidol. This is intended to ensure that the
glycidol remains in solution and only the alcohol formed
during the transes-terification is distilled off from the
reaction mixture.
As an upper limit, those solvents which have -the same ;^`
boiling point as glycidol (under 760 mm Hg = 162-lZ3C
(decomposition); under 13 mm Hg = 54C) are still suitable.
Possible solvents are, above all, aromatic hydrocarbons, such
as benzene, toluene, xylenep trimethylbenzene and chloro-
benzene. Fur-thermore 9 higher aliphatic e-thers, such as
dipropyl ether or dibutyl ether and diethylene glycol dimethyl
ether, cyclic ethers, such as dioxane and -trioxane, ketones,
7 --
-
,, . . ,, .. , , ~ , . .,; . ... ~. . .
. ,, , ; . ,: , ,, ~
~775~
such as methyl ethyl ketone, and cyclohexane, as well as
acetoni-trile or dlmethylformamide can also be used as
solven-ts. The solvent is appropria-tely employed in a 0.5-
fold to 10-fold amount by weigh-t, based on the total weight
of dicarboxylic acid dialkyl ester and glycidol.
The transesterification is carried out in a temperature
range of 50 to l20C. For the transesterification process
according to the in~ention, the reaction -tempera-ture is
preferably 6~ to 90~.
The thallium compounds used as transesterification
catalysts are preferably employed in a concentration of 10 2
to 10 3 mols per 1 mol o~ dicarboxylic acid dialkyl ester.
Suitable thallium compounds are -thalliu~ oxide, thallium
salts, thallium complex compounds and organo-thallium compounds
in which the Tl is bonded -to a C atom. In the process
according to the invention, thallium oxide, thallium-I
acetate or thalliumi-III acetate and, in particular, thallium
nitrate are preferably used as the transesteri~ication cata--
lyst~
Suitable polycarboxylic acid dialkyl es-ters are the
polyalkyl esters of aromatic, araliphatic, aliphatic, cyclo-
alipha-tic, heterocyclic, heterocyclic-aliphatic and he-tero- -
cyclic-aromatic polycarboxylic acids, especially dicarbo~ylic
acids, wherein the alkyl groups contain up to ~ C atoms.
The dimethyl esters and diethyl esters of aromatic or
aliphatic dicarboxylic acids are preferably used in the
process according to the inven-tion.
-- 8
, .
75~3
Sui-table alkyl es-ters are derived, for example, frorn
the polycarboxylic acids ~Jhich follow. Aromatic dicar~
boxylic acids which may be mentioned are: phthalic acid,
isophthalic acid, tereph-thalic acid, 2,5-dimethyltereph-thalic
acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,8-
dicarboxylic acid, naphthalene-2,3-dicarboxylic acid,
diphenyl ether 4,4'~dicarboxylic acid, diphenyl-L~,4'-
dicarboxylic acid and diphenyl~2,2'-dicarbox~lic acid~ tetra--
chlorophthalic acid and 2,5-dichloroterephthalic acid.
Aromatic tricarboxylic and tetracarboxylic acids which
may be mentioned are: benzenetricarboxylic acids1 such as
trimesic acid, trimellitic acid or hemi-mellitic acid,
benzenetetracarboxylic acidsS such as benzene~l,2,3,~tetra--
carboxylic acid, benzene-1,2,~,5-tetracarboxylic acid or
pyromellitic acid, benzophenone-~93',4,4'-tetracarboxylic
acid, naphthalenetetracarboxylic acid, perylenete-tracarboxylic
acid or tetracarboxylic acids o e the formula ~ `^
~OOC ~ X ~ ~ COOI~
llOOC COO~
wherein X represents a carbonyl, sulphonyl or methylene radi-
cal or an ether oxygen atom, such as, for example, benzo-
phenonetetracarboxylic acid.
Furthermore, the tetracarboxylic acids of the formula
. 9
~,
, , . ,,, , ,
,. ~ ~ ,. .. . . .... .. . ..... . . . .
~L~77~3
HOOC COOH
~- O -R -O - C ~ j
~ OOC . COO}I
wherein R represents the divalent radica-l of an unsubs-tituted
or substi-tuted glycol, which are obtainable by reacting 2 mols
o~ trimellitic anhydride Wi th 1 mol o~ a glycol are also
suitable.
Araliphatic dicarboxylic acids which may be mentioned
are: o-, m- and p-phenylenediacetic acid, ca-techol-O,O-
diacetic acid, hydroquinone-O,O-diacetic acid and resorcinol-
O,O-diacetic acid.
The dialkyl esters o~ the aliphatic dicarboxylic acids
can be derived ~rom ~msubstituted or alkyl-substituted and/or
phenyl-substituted saturated or unsa-turated aliphatic dicar~
boxylic acids. Examples of such dicarboxylic acids which
may be mentioned are: oxalic acid, malonic acid, succinic
acid, adipic acid~ 2,2 7 L~trimethyladipic acid and 2~4,4-
trimethyladipic acid as well as mixtures -thereof containing
the two isomers, sebacic acid, fumaric acid, maleic acid and
the dicarboxylic acids obtainable by an addition reaction of
acrylonitrile or acrylic acid esters and compounds with H
atoms which can be acti~ated, such as ketones, nitrogen com-
pounds, diols or dithiols.
Examples of cycloaliphatic dicarboxylic acids which
may be mentioned are: tetrahydrophthallc acid, methyl-
tetrahydrophthalic acid, isomerised 4-methyl-tetrahydro-
,
` ~7~5~3
phthalic acid, endomethylene~-te-trahydrophthalic acid, hexa-
hydrophthalic acid, methylhexahydroph-thalic acid, endo-
methylene-hexahydrophthalic acid, hexahydroterephthalic acid
and hexahydroisophthalic acid.
In addition, the dialkyl esters of dicarboxylic acids
which contain a heterocyclic ring, such as, for example,
thiophene-2,5-dicarboxyllc acid, furane-2,5-dicarboxylic acid 9
furane-3,4-dicarboxylic acid and pyrazine-2~3-dicarboxylic
acid and 19 3~bis-(carboxye'chyl)-hydantoin which is unsub-
stituted or substituted by alkyl in the 5-position, as well
as other dicarboxylic acid es-ters containing the hydantoin
ring, can also be used.
The polyglycidyl es-ters are liquid or solid and can be
purified by means of the customary methods, such as distilla- ~`
tion, extraction, sublimation and recrystallisation. In
many cases, however, purification of the products obtained
according to the process of the in~ention can be dispensed
with since the products are obtained in a relatively pure form
and meet the technical requirements. They are -therefore
suitable 9 in particular, for encasing or embedding elec~rical
or electronic components.
Example 1: Terephthalic acid diglycidyl ester
194 g ~1.0 mol) of dimethyl terephthalate are trans-
esterified with 177.6 g (2.4 mols) of glycidol in 1,200 ml of
m-xylene, in the presence of 2.9 g of thallium oxide, in -the
following apparatus: a packed column, on top of which a
reflux condenser A, which is hea-ted to 40C, is fitted, is
..... . ....... . . . . ... . . . . . .
10775~3
located on a reac-tion vessel fit-ted wi-th a stirrer and
therrnometer. The upper end of the reflux condenser is
cor~ec-ted via a bent glass tube -to a descending condenser B,
which is cooled with wa-ter at 15C; the receiver is cooled
in ice
The reaction mixture is now heated, in an oil bath,
whilst stirring, to an internal temperature of 80C and the
methanol formed is drawn, in the form of a vapour, under a
pressure of 100-120 mm Hg -through the hea-ted condenser A into
the condenser B, where it is condensed. m-Xylene refluxes
to the column from condenser A. Both at the star-t and at
the end of the reaction, the reac-tion mix-ture consists of a
pure solution in which the T1203 catalyst is suspended.
Samples are taken from the mixture from time to time and are
exarnined by thin layer chroma-tography. The course of the
reaction can be followed in this way.
After 1~ hours, no dimethyl terephthalate and only a
trace of the terephthalic acid methyl glycidyl diester, which
forms as an intermediate, can be detected. The catalyst is
filtered off from the warrn solution. The terephthalic acid
diglycidyl es-ter crys-tallises out of -the filtrate overnigh-t
in a refrigerator. It is fil-tered off and the filter cake
is washed with a lit-tle m-xylene and dried in a vacuurn
cabinet at 55~C.
216.7 g (77~9% of theory) of a product with a melting
point of 103-106C and an epoxide content of 6.75 equivalents
per kg (theory: 7.19) are obtained.
.. . . ..
~6~77~3
Fvrther diglycidyl terephthalate can be isolated from
the mother liquor as follows: in order to remove excess
glycidol, the solution is extracted with -three times 100 ml
o~ water and the solution is then concentra-ted -to dryness in
a rotary evaporator. Recrystallisat;ion of the residue
(61.5 g) from 300 ml of isopropanol gives a further 46.0 g of
a substance with a melting point of 103-106C and an epoxide
content of 6.90 equivalents per kg. The total yield of
terephthallc acid diglycidyl es-ter is thus 262.7 g (94.4% of
theory).
Example 2: Terephthalic acid diglycidyl es-ter
If the reaction is carried out according to the
i~structions of Example 1, but using freshly distilled
glycidol and a mixture o~ xylene isomers as the solvent,
222.7 g (~0.0% of theory) of a first fraction with a melting
point of 108C (epoxide content: 7.16 equivalents per kg) and
31.6 g (11.3% of theory) of a second fraction with a melting
point of 108C (epoxide content: 7.08 equivalents per kg)
are obtained.
Example 3: Tereph-thalic acid diglycidyl ester
194 g (1.00 mol) of dimethyl terephthalate are reacted,
in the apparatus described in Example 1, with 162.8 g (2.20
mols) of glycldol in 1,200 ml of m-xylene at 80C in the
presence of 2.90 g of T1203. After 24 hours no starting
material and only a trace of glycidyl methyl terephthalate can
be detected in the thin layer chromatogra~. The catalyst is
filtered of~ from the warm solution; on cooling, diglycidyl
'
~` 1C1775~3
terephthalate crystallises out. After cooling in a
refrigerator, filtering off and drying in a vacuum drying
cabinet at 65C, 222.7 g (80.~/o of theory) of a substance which
has a melting point of 101 - 105C and which contains 6.8~
epoxide equivalents per kg are obtained. The mother liquor
is extracted with three times 100 ml of H20 and concentrated
to dryness in a rotary evaporatorO Recrystallising the
residue twice from isopropanol gives a further 22.4 g (8.0D/o
of theory) of a product with a melting point of 100 - 103C
and an epoxide content of 6.72 equivalen-ts per kg.
ExamE~le 4: Terephthalic acid diglycidyl ester
97.0 g (0.50 mol) o:~ dime-thyl tereph-thalate are trans-
esterified, in the apparatus described in Example 1, with 14~ g
(2.00 mols) of glycidol in 500 ml of toluene at 80C in the
. .
presence of 1.47 g of T1203, the methanol which forms escaping,
under a pressure of 150-200 mm Hg, through the condenser which
is heated to 48C. A~ter a reaction period of 8-1- hours, no
dimethyl terephthalate and only a little glycidyl methyl
terephthalate can be detected in the thin layer chromatogram.
The catalys-t is filtered off from the warrn solution and, after
cooling, the solution is extracted, in a separa-ting funnel,
with three times 80 ml of water. Three phases form. The
aqueous phase is separated off and extracted twice more
with, in each case, 100 ml of toluene. After combining the
extracts wi-th the two organic phases first separated off 9 the
combined extracts are concentrated in a rotary evaporator at
a ba-th temperature of 60C and under a pressure of 10 mm Hg.
.
- 14 -
)77~3
125.9 g of a crude product with an epoxide content of 6.61
equivalents per kg are obtained. Recrystallisation frorn
650 ml of isopropanol gives 100.0 g (72.2% of theory) of
diglycidyl terephthalate with a melting point of 103-106C
and an epoxide content of 6.81 equivalents per kg.
Exam~ Terephthalic acid diglycicLyl ester
. . .
58.2 g (0 30 mol) of dimethyl -tereph-thalate are trans-
esterified, in the apparatus describecl in Example 1, with
53.3 g (0.72 mol) of glycidol in 360 ml of m-xylene at 80C in
the presence of 0.45 g of -thallium-I ace-tate. After a
reac-tion period of 15 hours, no starting material and only a
very little glycidyl methyl terephthalate C~l be de-tected.
The mixture is filtered to remove a slight turbidity and the
filtrate is extracted with three times 50 ml of H20. After
concentrating the solution in a rotary evaporator, the crude
product is recrystallised from isopropanol. 65.5 g (78.5%
of theory~ of a first fraction with a melting point of 103~
105C and an epoxide content of 6.86 equivalents per ~gy as
well as 13~6 g (16.3% of theory) of a second fraction with a
melting point of 100-102C and an epoxide content of 6.74
equivalents per kg are obtained.
Examples 6 to 21: Catalyst variations
If the reaction is carried out under the same con-
ditions as in Example 5 but, in place of Tl-I acetate~ equiva-
lent amounts of other -thallium compounds are employed, the
yields listed in the Table which follows are obtained:
.
- 15 - ~
~, .
.. . .. . . .. .. . . . . . . .. . . .. . .
~LO775~113
.
. .
o ~ o ~ ~ ~o o
rt (O Lr~ Lr~ ~ 03 rt 0
~1 . . . . . .
. ~D ~O ~O ~O ~O ~O ~ ~O
t I Ll _ .
-1' V
t~ ~100 ~D ~ t~J 1~ ~ ~O Lf~
t~l ~1 ~ o~ o o o
1~ ~ rtr-l rt ~O
rt-~l O t~ t~ O ~ t~
tL~ O t~ O t~t~ O t~ O O
~1 ~ ~ r~ r-l r~ rt ~1
t~J ~ .
a) c~ o ~ {~ O ~O
.~ Lr\t~ . r; t~
~æ rt~I t~ rt C~ rt
._ ~
;~ O t~l ~O 1:~
O O G~ a~ o
- - I 1
~ C`~ O ~O 1~ ~D
~ ~
O V .....___ __
It ~00 . .
~D 1~ 1~~O ~) 1
~ I Ll I I I I tl ;~
h rt rl O O O O O O
tl) O rt rt rtrt r~ rt
.~
rt rt _ _ _____
a) o ~1 ~D O ;l t~ ~ t~
~ r~t Lt~ ~ i~ t~ oO 0 L~
0 C~ O ~O t;O
-- ' -- . . ... . _ _ _ ._._ . A _. _ . _ _ _ _ _ _ . _ _ _ __ _ _. __ .
' h /--\~' t ~
~ ' ~ E~ ~
~ ~ O~
~) rt ~ ~ O ~ rt ~
E~ V
' ~y r-l
. . .... ___ . __ _ . . _ _
rt
~ ~D ~ 0~) (~ rt rt rt
~_ _ ,
-- 16 --
- . . . ,` , :: , . .,- `:. : :. . , . ,: . : -~:.. : . : -
7751D13
_ ~ ~ ~
~ o CO o ~ ~
o
__ t
~ ~ ~ C7~ 0 o ~ .,.
C~
~ ~1~_1 0 1_1 ~ r
...._ _ ~
' ~0 ~ '
~ 0~ 0 U~
r~ ~ ) 0 .
O ~_
__ _ ~:
S-~ C~ D I
;~' O g
r~ _ _
~ ~ ' 01 :~ '
_ - ' . .
- 17 -
- , . ~ . ~ ,.. .. . . . .. . . . ........... . . . .
~1~775~3
__ _
D
~ ~ ~ D
C~)bOr~ _ _
h r~l ~ ~1 0 0
~ ~ a~ l ,`
a) ~
_ 2R _ _ r
~X ~ ~o 0
1 '' _ _ _
~ ~ .
.~ rl~-l rl rl X
u~ :~ F4
r~ ~--
~i ~
æ - h
1 a
~3
l~3 .' .
-- 18
~0775~)3
~omparison xample
In accordance wi-th British Paten-t 1,118,206, 48.5 g
(0.25 mol) of dimethyl terephthalate were transes-terifiedl in
the appara-tus described in Example 1, wi-th 4~ g (0.~0 mol)
of glycidol in 300 ml of m-xylene at 80C in the presence of
Na methylate (prepared ~rom 0.086 g of sodium and 8.6 ml of
methanol). A polymeric solid produc-t was already deposited
on the walls of the flask af-ter a reaction period of 2 to 3
hours and the amount of this product increased greatly after a
total reaction period of 6 hours. After 6 hours, the
dissolved constituents of the reaction mixture were examined
to determine their epoxide content; this was 0.90 equivalent
per kg and had grea-tly decrea~ compared with -the value of 1.62
equivalen-ts per kg determined at the s-tart o:E the reaction.
It is true that after 6 hours only a little dimethyl
terephthalate could be detected in the thin layer chromatogram.
However, on the basis of the intensity of the chroma-togram
spo-ts, i-t was possible to show, in addition to the
desired diglycidyl terephthalate, the presence of about equal
amounts of the singly -transesterified diester, that is to
say tereph-thalic acid glycidyl methyl diester.
In comparison with -this9 the total epoxide content of
the solution increased,over the entire experimental period of
14 hours, from 1.60 to 1.74 equivalents per kg, in the case of
the process according to Example 1, which was carried out
according to the invention~ since methanol d~L~d o~f and, as
a result, the epoxide concentration increased. I~ the
~ 19 --
:,
1~775~3
figures are recalculated taking -the distillate in-to accoun-t,
the total epoxide con-tent remained cons-tant in Example 1.
Example 22: Ph-thalic acid diglycidyl ester
58.2 g (0.30 rnol) of dimethyl ph-thalate are trans-
esterified, in the apparatus described in Example 19 with 53.3
g (0.72 mol) of freshly distilled glycidol in 300 ml of m-
xylene at 80C in the presence of 0.82 g of Tl(OCOCH3)3.1-2-H20.
After 6-~ hours only -traces of meth~l glycidyl ph-thalate,
which was formed as an intermediate7 can be detected in the
thin layer chromatogram; no further dimethyl phthalate is
present. The solution is filtered to remove a sligh-t
turbidity, the filtra-te is extracted wi-th 5 times 40 ml of
water and th~ solution is concentrated in a ro-tary evaporator
at 70C under a water pump vacuum; 78.G g (94.2% of theor~) of
a crude product remainO A further 4, 4 g of product can
be isolated by extrac-ting the aqueous phases with chloroforrn
and are combined with the main amount. In order to remove
solvent residues, the product is after-treated in a distilla
tion apparatus with an air leak tube for one hour at 75C and
under a pressure of 0.01 mm Hg; residue: 80.8 g (theory:
98 6 g) of crude diglycidyl phthalate which is liquid a-t room
-temperature and has an epoxide content of 7.14 equivalen-ts per
kg (theory: 7.19 epoxide equivalents/kg).
For purification, 6035 g of the product are distilled
in a bulb tube oven under a pressure of 0.016 mm Hgo 5.33 g
of distillate are obtained (the bulk o~ this distils a-t an
oven temperature of 167 C); calculation shows this to corres-
- 20
:.
~L077S6)3 ;~
pond to a yield of 83.9% of theory,
Exarnple 23: Succinic acid diglycidyl ester
36.5 g (0.25 mol) of succinic acid dimethyl ester are
transesterified, as in Example 1, with 44.4 g (0.60 mol) of
glycidol in 300 ml of m-xylene at 80C in the presence of
0.73 g of T1203. After 9 hours no succinic acid dimethyl
ester and only a trace of the mixed ester can be detec-ted in
the thin layer chromatogram; The ca-talys-t is fil-tered off
from the warm solution and -the filtrate ls concentrated in a
rotary evaporator at a bath temperature of 60C, 58.6 g of the
crude product remaining.
Distillation of 6.20 g of the crude product in a bulb
tube oven under a pressure of 0.004 mm Hg and at an oven
temperature of at most 210C gives 4.62 g of distillate~ which
is more than 97% pure according to gas chro~atography.
Calculation shows the yield to be 76.0% of theory. The
produc-t solidifies in a crystalline form at room temperature
and has an epoxide content of 8.68 equivalents per kg (theory:
8.69)~ ;
2.0 g of the distilled product are recrystallised
twice from a 6-fold amount of isopropanol. Crystals with a
melting point of 56-60C are obtained.
Analysis: CloH1406 ~molecular weight = 230.22);
calculated: C 52.17 H 6.13
~ound . C 52.20 H 6.09
: Trimesic acid triglycidyl ester
50.4 g (0.2 mol) of trimesic acid trimethyl ester are
- 21 -
~775~3
reacted, in the apparatus described in Example 1, with 53,3 g
(0.72 mol) of glycidol in 360 ml of xylene (mixture o.~ iso-
mers) at 80C in the presence of 0,84 g of -thalli.um oxide,
After 7 hours, the thin layer chromatogram shows no further
trimesic acid trimethyl ester and only a trace of an in-ter
media-te produc-t which is not completely transes-terified9 the
reaction is discontinued after 10 hours.
The catalyst is filtered off from the warm solution,
After cooling, the clear yellowish filtrate is extracted by
shaking wi-th three times lO0 ml of distilled water5 by which
means excess glycidol is removed. The product phase is then
dried wi-th sodium sulphate and filtered and the solven-t is
evaporated in a rotary evaporator at a bath tempera-ture of
60C. The final solven-t residues are removed under a high
vacuurn at 60Co
Yield: 69.0 g (91,2% of theory) of crystalline tri-
mesic acid triglycidyl ester with a melting point of 74-77,5C
and an epoxide content of 8.0 equivalents/kg (100% of theory),
Microanalysis and the NMP, spectrum confirm the structure of
-the product.
Tri.mellitic acid triglycidyl ester
37.8 g (0.15 mol) of -trimellitic acid trimethyl es-ter
are reacted, in -the app~ratus described in Example l, with
40.0 g (0.54 mol) of glycidol in 270 ml of xylene (mix-ture of
isomers) at 80C in the presence of 0.63 g of thallium oxide.
After 14~ hours, the thin layer chromatogram shows no fur-ther
trimelli.tic acid trirnethyl ester and only traces of inter-
- 22 -
1~77503
mediate products which are incompletely transesterifie~ and
the reaction is discontinued.
The catalyst is filtered off from the warm solution.
As the filtrate cools, some of the product precipitates as an
oil. The oil is separa-ted of:E; the filtra-te (xylene
solution) and the Qil (taken up in 100 ml of chloroform~ are
separately further worked up in -the same manner: -the separate
solutions are extracted by shaking with three times 100 ml of
water, in order to remove excess glycidol, then dried with
sodium sulphate and filtered and the solvent is evaporated in
a rotary evaporator at a bath temperature of 60C and com-
ple-tely removed under a high vacuum at 60C.
Yield: 26.1 g (46.1% o~ theory) of -trimellitic acid
triglycidyl ester (A) are obtained, as a pale yellowish and
very sligh-tly turbid oil with an epoxide content of 7.85
equivalents/kg (99.05% of theory), from the xylene solution.
A further 12.7 g (22.3% of theory) of -trimellitic acid
triglycidyl ester (B) are obtained, as a yellowish oil with an
epoxide content of 6.40 equivalents/kg (80.7% of -theory),
from the fraction which precipitated as an oil.
Accordingly, -the total yield is 38.8 g (68.4% of
theory) and the epoxide content (average value) is 7.38
equivalents/kg (93.06% of theory).
: Trimelli-tic acid triglycidyl ester
50 4 g (0.2 mol) of trimellitic acid -trime-thyl ester
are reacted, in the apparatus described in Example 1, with
53.3 g (0.72 mol) of glycidol in 360 ml of xylene (mixture of
_ ~3 _
~77~6~3
\
isomers) at 80C in the presence of 0.45 g of thalli~lm-I
acetate. A~ter 7 hours, -the -thin layer chromatogram shows
no further trimellitic acid trimethyl es-ter and virtually no
~urther incompletely transesterified lntermediate produc-~, and
the reaction is discontinued.
The reaction solution is extracted by shaking with
three times 100 ml of water, in or~er -to remove the excess
glycidol and the catalyst, and the xylene phase ls dried with
sodium sulphate, filtered and evaporated in a ro-tary
evaporator at a bath temperature of 60C; the final solvent
residues are removed under a high vacuum a-t 60C. The
aqueous extracts con-tain an oily fraction which has sub-
sequently precipita-ted and this is taken up in 200 ml of
chloroform, washed with -twice 100 ml of water, dried with
sodium sulphate, filtered and evaporated at 60C.
Yield: 38.5 g (50.9% of theory) of trlmellitic acid
triglycidyl ester (A) are obtained, as a pale yellowish oil
with an epoxide con-tent of 8.0 equivalen-ts/kg (100% of -theory),
from the xylene solution. A further 19.8 g (26.2% of theory)
of trimellitic acid triglycidyl ester (B) are obtained, as a
yellowish oil with an epoxide content of 7.2~ equivalents/kg
(91.1+% of theory3 from -the fraction which precipi-ta-ted as an
oil.
Accordingly9 the total yield is 58.3 g (77% of theory)
and the epoxide conten-t (average value) is 7.75 equivalents/kg
(97.8% of theory).
- 24 -
.
.
~'775i~13
Example 27: Pyromelli-tic acid tetraglycidyl es-ter
62.05 g (0.2 mol) of pyromelli.tic acid -tetrame-thyl
es-ter are reacted, in the apparatus described in Example 1,
with 71.1 g (O.96 mol) of glycidol in L~80 ml of xylene
(mixture of isomers) at 80C in the presence of 1.12 g of
thallium o~ide. After 8~ hours, the thin layer chroma-togram
shows no fur-ther pyromellitic acid -tetrame-thyl es-ter and only
traces of incomple-tely transesterifiecL in-termediate produc-ts
and the reaction is discontinued.
The reaction solution is diluted with 600 ml of
chloroform, the catalyst is filtered off and, in order to
remove excess glycidol, the fil-trate is evaporated in a ro-tary
evaporator at a bath.-temperature of 60C and finally under a
high vacuum at 60C. The solid residue (92.6 g~ 96.7% of
theory) is dissolved in 300 ml of warm chloroform On
cooling, 61.6 g of colourless crystalline pyromellitic acid
tetraglycidyl es-ter (A) precipitate out; melting point up to
136C (no-t sharp); epoxide con-tent 8.36 equivalents/kg (100~
of theory). The mo-ther liquor is extracted by shaking wi-th
-three times 100 rnl o~ water and the product phase is drled
~ith sodium sulphate, filtered and evaporated, first in a
rotary evaporator and then under a high vacuum at 60C.
Yield: a further 23.5 g (24.6% of -theory) of pyromelli-tic
acid tetraglycidyl ester (B), as an almost colourless oil which
a~ter some time solidifies in a crystalline form; epoxide
content 7.67 equivalents/kg (91.7% of theory)
Accordingly, the to-tal yield is 85.1 g (89,h o~ theory)
- 25 -
.
. , ~ ., :. . ,. .: . .. ~-
~0775~3
and -the epoxide conten-t (average value) is 8.16 eguivalents/
kg (97.6% of theory)
Ex~n~ 28: Isophthalic acid digl-rcidyl ester
233 g (1 20 mols) of dimethyl isophthalate are trans-
esterified, as in Example 1, with 213 g (2.88 mols) of
freshly distilled glycidol in 1,200 ml of m-xylene at 80C in
the presence of 3.24 g of Tl(OCOCH3)3.1-2- H20, in the course of
6 hours. The reaction mixture is ex-trac-ted with -three times
200 ml of water and the xylene phase is concentrated in a
rotary evaporator and this gives 340 5 g of a residue which is
a~-ter-treated at 75C under a high vacuum, using an air leak
tube. Yield: 328 0 g (98.2% of -theory) of crude diglycidyl
isophthalate, which solidifies on cooling.
Epoxide content: 6.59 equivalen-ts per kg (theory:
7.19 epoxide equivalents/kg).
For further purification, 4.25 g of the crude product
are distilled in a bulb tube oven under 0.01 mm Hg and at a
maximum oven temperature of 200C. Yield: 3.49 g (80.5% of
theory~. 1.00 g of the distillate is recrys-tallised from a
mixture of 4 ml of cyclohexane and 3 ml of benzene.
Crystals which melt at 73-74C are obtained.
Analysis C14H1~06 (molecular weigh-t = 278.26);
calculated: C 60.430/o H 5.07%
found : C 60.46% H 5.14%
Exarn~ 9: Adipic acid diglycidyl ester
34.8 g (0 20 mol) of adipic acid dimethyl ester are
transesterified, as in Example 1, with 35.5 g (0.4~ mol) of
~ 26 -
.. .. . '::,'!: . ~, :.:." !' ` ' ~
~1~7qS~3
freshly distilled glycidol in 200 ml of m-xylene a-t 80C in
the presence of 0.51 g of Tl(OCOCH3)3.11 H209 the r~action
being followed by gas chromatQgraphy. After 10 hours, the
solution is filtered to remova -turbidity and extracted three
t~mes with 50 ml of wa-ter; the combined aqueous phases are
rinsed with 3 times 100 ml of m-xylene After drying the
xylene solution with Na2S04 and removing -the xylene in a
rotary evaporator, 48.3 g of a crude produc-t remain;
epoxide con-tent 6.31 equivalents per kg.
2.21 g of the crude produc-t are dis-tilled in a high
vacuum in a bulb tube oven and, under 0.05 mm Hg and a-t a
maximum -temperature of 200C, 1.75 g of distillate are obtained.
Calcula-tion shows this -to correspond to a yield of 74.1% of
theory; epoxide content: 7.58 equivalents per kg (-theory:
7.75 epoxide e~uivalents/kg).
The bulk of the crude product is dis-tilled in a
distillation apparatus a-t 161-163C / O.015 mm Hg. Yield:
63.2% of theory.
AnalYSiS C12H1806 (molecular weigh-t -- 258 27);
calculated: C 55.81 found: C 56.11
H 7.02 found: H 7 12
Analy-tical data obtained from the H-NMR spec-trum
agree wi-th the struc-tural formula for adipic acid diglycidyl
ester.
Recrystallising the distillate twice from a mixture of
cyclohexanone and benzene, it being necessary for the solution
to be sa-tura-ted at about 20C, gives, on cooling in a
- 27 -
775~3
refrigera-tor, crystals which af-ter drying at 30C in ~acuo
have a melting point of 43-47C~
E~ample 3Q: Oxali.c acid diglycidyl ester
20~.4 g (1.40 mols) of diethyl oxalate are trans-
esterified~ as in Example 1, with 248.5 g (3,36 mols) of
freshly dis-tilled glycidol in 1,400 ml of mesitylene at 80C
in the presence of 3.78 g of Tl(OCOCH~)3.12 H20, a pressure
of 60-80 mm Hg being required. The reaction is followed by
gas chromatography; it is complete af-ter 5 houLrs. The solu-
tion is filtered to remo~e turbidity, concentra-ted and
recrystallised from 1,100 ml of benzene. Yield: 150.6 g
(53.2% of -theory) of a crystalline produc-t with a melting
poin-t of 95-98C. The mother li~uor is extracted by sha~ing
wi-th four 100 ml por-tions of water, the water is extracted
with benzene and the organic phase is added to the main
amount of benzene phase~ After concen-trating to 270 ml, a
further 47.4 g (16.7% of theory) of a crystalline produc-t
with a melting point of 87-92C crystallise o~t.
Analysis: C8Hl0o6 (molecular wei.gh-t = 202016);
calculated: C 47,5~ H 4,99
found : C 47.5 H 5.0
The analytical data obtained from the H-NMR spectrum
agree with the structural formula for oxalic acid diglycidyl
ester.
Oxalic acid diglycidyl es-ter
29,2 g (0,20 mol) of dlethyl oxalate are trans-
esterified, as in Example 1, with 35.5 g (0.48 mol) of freshly
- 2~
... . . . . . . .. .. ... . ...
756~3
distilled glycidol in 200 ml of chlorobenzene at 80C, in
the presence of 0.54 g of Tl(OCOCH3)~ H20, under pressure,
the pressure being maintained a-t 120~140 mm Hg. The reac-
tion is followed by gas chroma-tography and is already com-
plete after 4 hours. On cooling, the product crys-tallises
out from the solution and is filtered off, washed with hex-
ane and dried ln ~acuo at 55C. Yield: 26.2 g (64.8% of`
theory) of a crystalline product with a melting point o~ 86
96C and an epoxide conten-t of 9.50 equivalents per kg
(theory: 9 90 epoxide equivalents/kg)
The mo-ther liquor is extracted with four -times 40 ml
of H20 and the organic phase is then concentra-ted in a rotary
evaporator The residue (9.7 g) is recrystallised from 50 ml
of isopropanol. Yield: 6.8 g (16.9% of theory) of a crys-tal-
line product with a mel-ting point of 77-83C and an epoxide
content of 9.62 equivalents per kg.
Oxalic acid diglycidyl ester
244.6 g (1.21 mols)of dibutyl oxala-te are trans-
esterified, as in Example 1, with 214.8 g (2.90 mols) of
freshly distilled glycidol in 1,200 ml of mesi-tylene a-t 80C
and under a pressure of 60-80 mm Hg, in the presence of
3.27 g of Tl(OCOCH3)3.1~ H20. The reaction i5 followed by
gas chroma-tography; it proceeds relatively slowlyO After a
reaction -time of 24 hours, the reaction solu-tion is fil-tered,
concentrated and recrystallised from 400 ml of benzene~ The
crystalline product is filtered off, washed with benzene and
hexane and dried in vacuo a-t 55C Yield: 44.7 g of a
- 29 -
~C~7~7503
crys-talline produc-t with a mel-ting point of 86-89C and an
epoxide content of 9.26 equivalents per kg (-theory: 9,90
epoxide equivalents/kg).
: Malonic acid diglycidyl es-ter
66,o g (0,50 molj o~ malonic acid dimethyl ester are
transesterified, as in Example 1, with 88,8 g (1,20 mols) of
freshly distilled glycidol in 450 ml of m-xylene at 80C in
the presence of ].35 g of T1(0COCH3)3.l-2- H20 in the course
of 5 hours, No dimethyl ester and only a very lit-tle of -the
methyl glycidyl ester which is formed as an intermediate can
then be detected by gas chroma-tography: the main component
consists of malonic acid diglycidyl es-ter, On cooling, the
product separates ou-t as an oil. The xylene is removed in a
rotary evapora-tor, the residue is dissolved in benzene and the
solution is extracted with four 50 ml portions o~ wa-ter. The
aqueous phases are extracted with twice 60 ml of benzene.
All the benzene phases are combined and then concentrated in
a rotary evaporator at 60C, 94.3 g of an oily crude product
with an epoxide content o~ 8,22 equivalents per kg ~theory:
9.26 epoxide equivalents¦kg) are ob-tained.
For analytical purposes, 7,66 g of -the crude product
are distilled under a high vacuum in a bulb tube oven at
140C and under a pressure of 0.014 mm Hg, Yield: 6.12 g.
Analysis: CgH1~06 (molecular weight = 216.19)
Calculated: C 50.00 H 5,60
Found : C 49,94 H 5,61
The analytical da-ta obtained ~rom the H-NMR spec-trum
- 30 -
10775~3
agree with the structural formula for malonlc acid diglycidyl
ester.
Exam~le ~4: Sebacic acid diglycidyl ester
46.o g (0.20 mol) of sebacic acid dimethyl ester are
transesterified, as in Example 1, wtih 35.5 g (0.48 mol) of
freshly distilled glycidol in 200 ml of cyclohexanone at 80C
in the presence of 0.51 g of Tl(OCOCH3)3.1~ H20 and -the reac-
tion is followed by gas chromatography. After 24 hours, the
reaction solution is worked up by filtering it to remove tur-
bidity, extracting the filtrate wlth four 40 ml portions of
water and concentrating the organic phase in a rotary
evaporator.
After removing low-boiling fractions up to a boiling
poin-t of 90C under 0.012 mm Hg, 64.6 g of a crude product
which has an e~oxide content of 5.40 equivalen-ts per kg
(theory: 6.32) and which solidifies slowly at room tempera-
ture, are obtained as a residue.
A small amoun-t of this product is distilled under a
high vacuum in a bulb tube oven and 1.0 g of -the distillate
is recrystallised from 9 ml of a mix-ture of 90 par-ts of cyclo-
hexane and 10 parts of isopropanol~ Crystals wi-th a mel-ting
point of 42-43C are obtained.
Analysis C16H2806 ~olecular weight = 316.
calculated: C 60.74 H 8.92
found : C 60.78 H 8.43
Fumaric acid diglycidyl ester
43,2 g (0.30 mol) of fumaric acid dime-thyl ester are
,
.. . . . i. . .: . ., .;.. , .. , .. ,,. i. ,;, . ., . . . .... . .. , . , . ; .
~L0775Q3
transes-terified, as in Example 1, with 53.3 g (0.72 mol) of
freshly distilled glycidol in 250 ml of m-xylene at 60C in
the presence of 0.53 g of TlOCOCH~ and the reac-tion is fol-
lowed by gas chromatography. The transesterification already
proceeds very rapidly at 60C and is complete after 6 hours.
The solution is fil-tered to remove turbidity, the filtra-te is
extracted ~ith four 40 ml portions of water and the organic
phase is then concentra-ted in a ro-tary evaporator.
The a~ueous phases are extracted with three portions
of chloroform, the ex-tracts are concentra-ted and the two resi-
dues are combined Yield of crude product: 72.0 g of the
product which is solid at room -temperature.
For purification, 5 00 g of the crude produc-t are
distilled in a bulb tube oven under 0.01 mm Hg and at a
maximum oven temperature of 180C; yield: 4.12 g (86.6% of
theory) with an epoxide content of 8.56 equivalents per kg
~theory: 8.76).
After recrystallisa-tion from e-thanol, -the pure pro-
duct melts at 76-80C.
Analysis CloH1206 (molecular weigh-t = 228.20)~
calculated: C 52.64 H 5.30
found : C 52 69 H 5.40
: 3,3',4,4'-Benzophenone-te-tracarboxylic acid
te-traglycidyl ester
62.2 g (0.15 mol) of 3,3',4,4'-benzophenone-te-tra-
carboxylic acid tetramethyl ester are reacted~ in the appara-
tus described in Example 1, with 53.3 g (0.72 mol) of
- 32 -
;: .
77S~)~
glycidol in 360 ml of xylene (mixture of isomers) a-t 80C in
-the presence of 0.84 g of thallium oxide. After 14 hours,
the thin layer chromatogram shows no fur-ther starting mate
rial and only a lit-tle of the incompletely transesterified
intermediate product and the reaction is discontinued.
The reaction mixture contains an oily fraction7 which
is separated of~ and worked up separately.
The xylene solution is filtered to remove -the cata~
lyst and, in order to remove -the excess glycidol, is ex-trac-
ted by shaking with three times lO0 ml of wa-ter and the
organic phase is -then dried wi-th sodium sulphate and subsequently
filtered The solvent is evaporated in a rotary evapora-tor
at a bath -temperature of 60C and is removed completely under
a high vacuum a-t 60C
The oily fraction is taken up in 200 ml of chloroform
and the solution is filtered -to remove the catalyst and -then
worked up in the same way as the xylene solu-tion
Yield: 6 3 g (7~2% 0~ theory) of benzophenone
(-te-tracarboxylic acid tetraglycidyl es-ter) (A) are obtained,
as a yellowish oil wi-th an epoxide conten-t of 6 39 equivalen-ts/
kg (93% of theory), from the xylene solution A further
73~4 g (84% Of theory) of benzophenone-te-tracarboxylic acid
tetraglycidyl ester (B) are ob-tained, as a honey-coloured
oil, from -the fraction which precipitated as an oil. Epoxide
con-tent: 6.65 equivalents/kg (96,8~6 of -theory).
Accordingly, -the total yield is 79~6 g (9lol~ of
theory) and the epoxide content (determined ~y alligationj
~ 33 ~
~7~5~3
is 6.63 equivalents/kg (96,5% of -theory).
Exam~le_~Z~ Me-thylene-bis-[3-(p--glycidyloxycarbonyl-
benzyl)-5,5-dimethylhydantoin~
30.0 g (0.053 mol) of 1~1-methylene-bis-[3-(p-
methoxycarbonylbenzyl)-5,5-dimethylhydantoin~ are trans-
esterified, as in Example 1, with 9.4 g (0.13 mol) of freshly
dis-tilled glycidol in 200 ml of m-xylene at 80C in the pre-
sence of 0.14 g of Tl(OCOCH3)3 . 1~ H20. After 8 hours,
starting material can still be detected, in addition to -the
two reac-tion products (the me-thyl glycidyl ester and the di-
glycidyl ester) in -the -thin layer chromatogram. A little
polymeric material is filtered off and a further 9,4 g of
glycidol and 0.14 g of Tl(OCOCH3)3 . 1~ H20 are added -to -the
filtrate and the reaction is allowed -to proceed for a further
6-~ hours. Thereaf-ter 9 only small amounts of the methyl
glycidyl ester can be detected in the -thin layer chromato-
gram; all of -the star-ting material has been conver-ted~ The
solution is filtered to remove turbidi-ty, -the filtra-te is
concentrated, dissolved in 200 ml of CHC13 and extracted with
~our times 50 ml of water. After concentra-ting, 24.5 g of a
highly viscous crude product are o~-tained. In order -to remove
solvent residues, 5.1 g of the produc-t are after-treated at
100C and under a pressure of 0.1 mm Hg. Residue: 4.49 g
of a glassy mass with an epoxide conten-t of 2.60 equivalents
per kg (theory: 3.08 epoxide equivalents/kg)
y is: C33H3601o (molecular welght 648 67)
_ 34 _
~775~3
calculated: C 61.10 H 5 59 N 8.64
found : C 60.2 H 5.7 N 8.0
The H-NMR spectrum is in accord with the following
s-tructural formula:
C ~ C~C~200C ~ ~ COOC~I~C~ GH2
E me~ : N,N'-Bis-(p-glycidyloxycarbonylbenzoyl~-
isophorone-diamine
29.0 g (o.o6 mol) of N,N'-bis-(p-me-thoxycarbonylben- .
zoyl)-isophorone-diamine are -transes-terified, as in Example
1, with 10.5 g (0.14 mol) of freshly dis-tilled glycidyl in
150 ml of cyclohexanone at 80C in the presence of 0.13 g
of Tl(OCOCH3)3 . lj~- H20. After a reac-tion period of 24
hours, no further star-ting material can be detected in the
thin layer chromatogram; the methyl glycidyl ester is still
present in small amounts; The solution is filtered, th.e fil-
trate is extrac-ted with 3 times 30 ml of wa-ter and -the orga-
nic phase is concen-tra-ted in a rotary evaporator, whereupon
51.1 g of a reac-tion produc-t which still con-tains cyclohexa
none remain.
For analytical inves-tiga-tions, 7.1 g of.the resul-ti.ng
product are after-trea-ted for 2 hours at 100C and under a
pressure of 0.08 mm Hg in order to remove the residual cyclo-
hexanone ~.6 g of a glassy produc-t with an epoxide con-ten-t
of 2.84 equivalen-ts per kg (theory: 3.46 epoxide equivalen-ts/
~ 35 -
., . .: : ::. ,,: : :: . , :: , :, . .
~0775~3
kg) are ob-tained.
Analysis: C32~38N20~ (molecular weight _ 578,66)
calcula-ted: C 66.42 H 6.62 N 4.84
found : C 66.7 H 6.8 N 4.5
The H-NMR spectrum agrees with -the following struc~
tural formula:
O . O O O O n
CH2~CH-CH2~c-c ~ ~ ~'~`~ 2 ~I C_/~/~ C-O-CH2-CH-CII2
C ~ C~I3
E mple 3~: Cyclohexanone-2,2,6,6-te-trapropionic acid tetra-
glycidyl es-ter
44,3 g (0,10 mol) of cyclohexanone-2,2,6,6-tetra-
propionic acid tetramethyl ester are transes-terified, as in
Example l, with 35.5 g (0,48 mol) of freshly dis-tillëd
glycidol in 200 ml of m-xylene at 80C in the presence of
0.55 g o~ Tl(OCOCH3)3 , l-~ H20 and the course of -the reac-tion
is followed by a thin layer chromatogram. I-t can be shown
: that -the reac-tion proceeds, via the expec-ted mixed
esters, to the -tet~aglycidyl es-ter. Af-ter only 3-z
hours, only small amounts of -the methyl triglycidyl ester can
be detec-ted and the te-traglycidyl ester separa-tes out of -the
originally clear solu-tion as an oil. The reaction mixture is
concentrated in a rotary evaporator and dissolved in 250 ml
of chloroform, the solution is extrac-ted with 4 times 40 ml
of H20 and -the solu-tion is again concentrated, After subject~
ing -the residue to an after-treatmen-t at 100~ under a vacuum
- 36 -
. , .
. ., . .. ,., ,., , . ,-" , , , , ", ; ,,, , , , ,, ,,;
1C)77S03
of 0.09 mm Hg, 48.9 g (80.3% of -theory) of a highly viscous
crude produc-t ~Tith an epoxide con-ten-t of 5.58 equivalen-ts per
kg (-theory: 6.55 epoxide equivalents/kg) are obtained.
Ana~ysis: C30~I42013 (molecular ~eigh-t = 610.65)
calculated: C 59.01 H 6.93
found : C 59.3 H 7.0
The analy-tical data obtained from the H-NMR spectr~n
confirm that the product obtained has the following struc-
-tural formula: .
' ~
r~R , / \
0 R= -CU2CII2-C 0-C ~-C~-LII2
' ' ' ' ;'.'
,
- 37 -
- ~ . ... ... .... . . . . . . . .. . .
~ ' i ' .; , . - - '; ~ ; '.. ,.,,: ,, '' . ., . ,, ,,, .,. "
.. ,...... . : ~, . , . : ,, .. , ,.. " ., .:, .. , , . .. ,:
,, .: , , ,: ... .. . :,: : , . .:: . :: . .... . .
. : . .: :. - , :: ,:: ,.. . . , ~ . . . : ,
. . . . . .... .
