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Патент USA US3078291

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B?'liiidd
Patented Feb. 19, 12%3
l
2
3 07%,289
present invention, the reaction equation for the formation
of the dimeric compound is given hereina?ter as follows:
PGLYMERHZATIQN PilGDUCTS 9F EPEHALGGEN
(BHYDRINS (IQNTAINENG AN EPOXY GROUP EN
alga/int MQLEC‘ULE AND PRQCESS 6F MAKING
E
Theodor Ploetz, Hcesel, Kreis Mettmann, and Hermann
Richtzenhain, Koln-duellz, Germany, assignors to Field
muehie, Papier- and Zellsto?werhe Alitiengesellschai‘t,
The known polymerization products obtained by using
Duesseidor 'u?herltassel, Germany, a company of Ger
boron triiluoride, aluminum chloride, stannic chloride and
10 the like catalysts have an entirely di?erent con?guration
and contain only polyether chains as is evident from the
following structure:
many
No Drawing. Filed Dec. 16, 1959, Ser. No. 35%,855
Claims priority, application Germany Dec. 22, 1958
11 (Ziaims. (Cl. 269-343)
The present invention relates to new low molecular
15
polymerization products of epihalogenohydrins contain
The amount of the catalytically active compound used
ing an epoxy group in their molecule, and to a process of
in the polymerization process according to the present
making the same.
invention can be varied Within Wide limits. In general,
Processes are known according to which epichlorohy
amounts between 1% and 20% are used and amounts of
drin and other compounds containing an epoxy group in
their molecule can be polymerized with the addition of 20 about 10% of the weight of the epihalogenohydrin reacted
are suirlcient. The activity of the catalytically eifective
catalytically active agents, such as boron tri?uoride, alu
compounds as far as they are insoluble in the epihalogeno
minum chloride, stannic chloride, and the like. The
hydrin, depends not only upon their chemical nature but
polymerization products obtained thereby are free of
also upon the nature of their surface. Compounds hav
epoxy groups.
ing the largest surface area per unit of weight have proved
It is one object of the present invention to provide new
to be most e?ective.
low molecular polymerization products of epihalogeno
Reaction of the epihalogenohydrin is carried out at
hydrins w ich still contain an epoxy group in their mole
moderately increased temperatures. Generally tempera
cule.
tures between 100° C. and 200° C. are su?icient. The
Another object of the present invention is to provide
new and valuable polymerization products containing the 30 reaction can be carried out in continuous operation
whereby, of course, uniform distribution of the catalyst
functional epoxy group and halogen atoms in their
in the epihalogenohydrin must be effected.
molecule.
The epihalogenohydrin mentioned above as starting
materials can be co-polyrnerized with other epoxides oi
Still another object of the present invention is to pro
vide a simple and eiiective process of producing such
35 the formula
polymerization products.
These and other objects of the present invention and
advantageous features thereof will become apparent as
the description proceeds.
According to the present invention it has been found
40
that epihalogenohydrins having the general formula
Ra
in which R3, R4, R5, and R6 represent hydrogen or alkylv
radicals and more particularly lower alkyl radicals with
as
l to 5 carbon atoms.
The resulting polymerization products are, for instance,
valuable plasticizers and stabilizers, for instance, for poly
vinyl chloride, chlorinated rubber, and the like chlorine
containing plastics. The functional groups present
R1 and R2 are hydrogen, alkyl radicals, cycloalkyl radi
cals, or aryl radicals and preferably lower alkyl radicals
with 1 to 5 carbon atoms or the phenyl radical which 50
therein, i.e. the halogen atoms and the epoxy group render
may be substituted by lower alkyl radicals and/or which
them suitable for further reactions.
The following examples serve ‘to illustrate the present
invention without, however, limiting the same thereto.
In these examples the amounts are given in parts by
may be hydrogenated, while
X is halogen and preferably chlorine,
can be polymerized in a completely different manner by
heating such epihalogenohydrin compounds with catalyti
cally active compounds of metals of the second group of
the periodic system, preferably with the oxides, carbonates,
basic carbonates, silicates, and chlorides of magnesium or
zinc or with mixtures of such compounds.
55
Weight.
Example 1
100 parts of epichloro-hydrin and 8 parts of basic mag
nesium carbonate MgCO3.Mg(OH)2 are heated to 120°
C. for 48 hours While stirring. The catalyst is ?ltered
In contrast to the heretofore known polymerization 60 off, washed with epichlorohydrin and is again used in
products of epihalogenohydrins which do not contain an
a new batch. Unreacted epichlorohydrin is distilled olf
epoxy group in their molecule, the products prepared ac
from the yellowish ?ltrate. 89 parts of a polymer mix
cording to the present invention still contain such an
ture are obtained fro-m which the following polymers can
epoxy group. As is evident from the following examples,
be isolated by repeated fractional distillation in a vacuum:
65
the new polymerization products consist mainly of di
(a) 36% of pure dimeric epichlorohydrin. Colorless
meric and trimeric epihalogenohydrins. In order to illus
liquid, boiling point: 81° C./().3 mm; nD2°=1.4767.
trate the composition of the products according to the
scrapes‘
4
3
the high molecular polymer while a lower polymeriza
tion temperature prolongs the polymerization time very’
considerably. Temperatures below 100° C. are in gen“
Analysis:. C6H10O2Cl2: Calculated: 38.9% C; 5.4% H;
38.3% Cl; epoxide equivalent: 185. Found: 38.8%
C; 5.4% H; 38.2% C1; epoxide equivalent: 187.
(b) 28% of pure trimeric epichlorohydrin. Light yel
low viscous liquid; boiling point: 154—160° C./0.3
mm.; nD2°=1.4902. Analysis: C9H15O3Cl3: Calcu~
lated: 38.9% C; 5.4% H; 38.3% C1; epoxide equiva
eral unsuitable.
As stated above, the new polymerization products are;
valuable plasticizers and stabilizers for chlorine‘ conta1n-'
ing polymers. They exhibit in this respect a similar:
behavior as the liquid epoxies. They may also be'usedt
as intermediates in the manufacture of glycidol-like com-'
lent 277.5. Found: 38.7% C; 5.6% H; 38.0% Cl;
epoxide equivalent: 282.
(c) 23% of an intermediate fraction which can be re 10
cycled and added, when distilling further batches.
(d) 12% of a very viscous residue consisting of higher
groups. Furthermore, they. are useful as one of the reac
tion components in the manufacture of epoxy resins
whereby they may replace epichlorohydrin partly or com
polymers of epichlorohydrin; boiling point: 200° C./
0.1 -mm.; epoxy equivalent: >1075.
Example 2
pounds 'by replacing the chlorine atoms by hydrox'yb
pletely.
15
Of course, many changes and variationsmay be made
in the reaction conditions, temperature and duration, in
100 parts of epichlorohydrin and 10 parts of zinecar
the catalysts used in the methods of working up the
bonate are heated to 120° C. for 48 hours while stirring.
polymerization products and of isolating the duneric,
On working up the reaction mixture according to Ex
ample 1, 21 parts of a mixture of crude polymerization‘ 20
products are obtained from which the corresponding pure
fractions (a) to (d) are obtained by fractional distilla
trimeric, and polymeric reaction products'from the polym
tion in a vacuum.
erization mixture, and the like in accordance with the
principles set forth herein and in the claims annexed
hereto.
We claim:
_
1. The dimeric polymerization product of epichloro
Example 3
100 pads of epichlorohydrin and 20 parts of mag 25 hydrin of the formula
nesium silicate are heated to 120° C. for 48 hours While
C1H2C—CH—~O—-CHz—-CH——-CH1
stirring. On working up the reaction mixture according
to Example 1, 10 parts of a mixture consisting of crude
lbeinga colorless liquid having a boiling point of about
11201
0/
polymerization products are obtained from which the
81° C./ 0.3 mm. and an index of refraction nD2°= 1.4767.
corresponding pure fractions (a) to (d) can be obtained. 30 2. The trimeric polymerization product of epichloro
by fractional distillation in a vacuum.
hydrin of the formula
Example 4
ClHzC-CH—-O—-OHz—CH—O-—CH2~—CH7CH2
H201
b13201
0
100 parts of epichlorohydrin and 1 part of anhydrous
magnesium chloride are heated to 120° C. for 48 hours 35 being a light yellow viscous liquid having a boiling point
while stirring. After ?ltering off a small amount of un
of about 154-160° C./O.3 mm. and an index of refraction
dissolved matter, excess epichlorohydrin is distilled off.
n92": 1.4902.
41 parts of a mixture consisting of crude polymerization
3. The polymerization product of epichlorohydrin con
products are obtained from which the pure fractions (a)
taining
a termianl epoxy group of the formula
40
to (d) are obtained by fractional distillation in a vacuum.
——O-—-OH:—CH————CH:
In place of epichlorohydrin as used in the preceding
\o/
examples, there maybe employed equimolecular amounts
of other epihalogenohydrins such as epibromohydrin and
epiiodohydrin while otherwise the procedure is the same
as described in said examples. Likewise, other epichlo
a terminal methyl substituted. by two chloro methyl
groups, said substituted terminal methyl group being of
the formula
rohydrins wherein R1 and/or R2 are alkyl, cycloalkyl,
morn-0H
or aryl radicals, such as 1,2-epoxy butylchloride-(3);
2-methyl-1,2-epoxy propylchloride-(3); 2-phenyl-1,2
H201
epoxy propylchloride-(3); 1,2-epoxy-3-phenyl propylchlo
ride~(3); Z-methyI-S-phenyl-1,2-epoxy propylchloride-(3)
and others can be used as starting material.
50
Epichloro
and intermediate units forming the polymer chain of the
formula
hydrin, however, is the preferred reactant due to its ready
availability and low price.
CHzCl
In place of zinc carbonate and the magnesium salts
used as catalysts in the preceding examples, there may 55 said polymerization product being a viscous product of
the boiling point of‘about 200° C./ 0.1 mm.
be employed the same amounts of other catalytically
4. The copolymerization product of an epihalogenohy
effective compounds of metals of the II group of the
driu of the ‘formula
periodic system, such as magnesium oxide, zinc oxide,
zinc chloride, or the corresponding alkaline earth metal
R1 1'}:
compounds, or cadmium. compounds. Magnesium and 60
capo-0H2;
\ /
zinc compounds, however, have proved to be especially
suitable and are the preferred catalytic agents.
Epoxides which may be added during polymerization
of the epihalogenohydrins according to the present inven
tion and Whichyield valuable copolymerization products 65
are, for instance, ethylene oxide, propylene oxide, tri
methylene oxide, tetrahydrofuran, 1,2-epoxy butane,
2-methyl~l,2-epoxy butane, pentamethylene oxide, 2,3
0
wherein
R1 and R2 indicate members selected from the‘group
consisting of hydrogen, lower alkyl, phenyl, cyclo
hexyl, and phenyl and cyclohexyl substituted by lower
alkyl, and
X indicates a halogen selected from the group consist
epoxy pentane, styrene oxide, 2-phenyl-1,2-epoxy pro
ing ofchlorine, bromine, and iodine,
pane, and others. By varying the amounts of the epoxide 70
compounds added to the polymerization mixture it is
and an epoxide of the formula
possible to vary the properties of the resulting copolym
R4
R5
erization products.
The preferred reaction temperature is a temperature
\ /
of about 120° C. Higher temperatures produce more of 75
0
Rr-J§-——(lJ—Ra
3,078,280
_
6
55
wherein
R3, R4, R5, and R6 indicate members selected from
the group consisting of hydrogen and a lower alkyl,
wherein
R3, R4, R5, and R6 indicate members selected from the
group consisting of hydrogen and lower alkyl,
said copolymerization product containing a terminal epoxy
group in its molecule, said copolymerization product being
produced by heating a mixture of said epihalogenohydrin
said copolymerization products having a terminal epoxy
group in their molecule, the step which consists in heat
ing a mixture of said epihalogenohydrin and said epoxide
at a temperature between about 100° C. and about 200°
C. with the addition of a catalytically active compound
active compound selected from the group consisting of the 10 selected from the group consisting of the oxide, car
bonate, basic carbonate, silicate, and chloride of a metal
oxide, carbonate, basic carbonate, silicate, and chloride
of the second group of the periodic system for a period
of a metal of the second group of the periodic system
of time sut?cient to produce a liquid copolymerization
for a period of time suf?cient to produce a liquid c0
product but insu?icient to cause formation of a solid
polymerization product but insu?icient to cause forma
tion of a solid product.
15 product.
and said epoxide at a temperature between about 100° C.
and about 200° ‘C. with the addition of a catalytically
8. In a process of producing liquid polymerization
products of an epihalogenohydrin of the formula
5. In a process of producing liquid polymerization
products of an epihalogenohydrin of the formula
R1 R2
I
mow 4: -CHX
20
0
0
wherein
R1 and R2 indicate members selected from the group
wherein
R1 and R2 indicate members selected from the group
consisting of hydrogen, lower alkyl, phenyl, cyclo
hexyl, and phenyl and cyclohexyl substituted by
consisting of hydrogen, lower alkyl, phenyl, cyclo
hexyl, and phenyl and cyclohexyl substituted by
lower alkyl, and
lower alkyl, and
X indicates a halogen selected from the group con
X indicates a halogen selected ‘from the group con
sisting of chlorine, bromine, and iodine,
sisting of chlorine, bromine, and iodine,
said polymerization products having a terminal epoxy
30
said polymerization products having a terminal epoxy
group and terminal methyl, its carbon atom carrying two
group and a terminal methyl carrying two
~—(|3HX groups
“(EEK groups
R2
the step which consists in heating said epihalogenohydrin
In
35 the step which consists in heating said epihalogenohydrin
at a temperature between about 100° C. and about 200°
C. with the addition of catalytically active basic mag
at a temperature between about 100° C. and about 200°
C. with the addition of a catalytically active compound
nesium carbonate for a period of time su?icient to pro
duce a liquid polymerization product but insu?cient to
selected from the group consisting of the oxide, carbonate,
basic carbonate, silicate, and chloride of a metal of the 40 cause formation of a solid polymerization product.
9. In a process of producing liquid polymerization
second group of the periodic system for a period of time
products of an epihalogenohydrin of the formula
su?icient to produce a liquid polymerization product but
insu?icient to cause ‘formation of a solid polymerization
R1 R2
product.
6. In a process of producing liquid polymerization
products of epichlorohydrin, said polymerization prod
HZG——'&‘-(IJHX
\ /
45
ucts having a terminal epoxy group and a terminal methyl
0
wherein
carrying two chloro methyl groups, the step which con
R1 and R2 indicate members selected from the group
sists in heating said epichlorohydrin at a temperature
consisting of hydrogen, lower alkyl, phenyl, cyclo
between about 100° C. and about 200° C. with the addi
hexyl,
and phenyl and cyclohexyl substituted by
50
tion of a catalytically active compound selected from
lower alkyl, and
the group consisting of the oxide, carbonate, basic car
X indicates a halogen selected from the group con
bonate, silicate, and chloride of a metal of the second
sisting of chlorine, bromine, and iodine,
group of the periodic system for a period of time suffi
said polymerization products having a terminal epoxy
cient to produce a liquid polymerization product but
group and terminal tmethyl, its carbon atom carrying
insuf?cient to cause formation of a solid product.
7. In a process of producing liquid coopolymerization
two
products of an epihalogenohydrin of the formula
——(%HX groups
R1 R3
rrzO—~——<lJ—drrX
\ /
R2
60 the step which consists in heating said epihalogenohydrin
at a temperature between about 100° C. and about 200°
0
wherein
R1 and R2 indicate members selected from the group
consisting of hydrogen, lower alkyl, phenyl, cyclo~
hexyl, and phenyl and cyclohexyl substituted by
C. with the addition of catalytically active zinc carbonate
for a period of time suf?cient to produce a liquid polym
erization product but insuf?cient to cause formation of
65 a solid polymerization product.
10. In a process of producing liquid polymerization
products of an epihalogenohydrin of the formula
lower alkyl, and
X indicates a halogen selected from the group con
sisting of chlorine, bromine, and iodine,
and and epoxide of the formula
Ilia
R1 R1
70
0
wherein
R1 and R2 indicate members selected from the group
Ra
Rr-O<-—/é~R?
o
H2C——-—dl—élHX
\ /
75
consisting of hydrogen, lower alkyl, phenyl, cyclo
3,078,280‘
8
hexyl, and phenyl and cyclohexyl substituted by
lower alkyl, and
group and terminal methyl, its carbon atom carrying
1W0
X indicates a halogen selected from the group con
—-CHX groups
sisting of chlorine, bromine, and iodine,
2
said polymerization products having a terminal, epoxy 5 the step which consists in heating said epihalogenohydrin
group and terminal methyl, its carbon atom carrying
to about 120° C. for about 48 hours while stirring.
two '
-—CHX groups
a
10
the step‘ which consists in heating said epihalogenohydrin
References Cited in the ?le of this patent
UNITED STATES PATENTS‘
2,106,347
2,498,195
at a temperature between about 100° C. and about‘ 200°
C. with the addition of catalytically active magnesium
chloride for a period of time su?icient to produce a liquid
polymerization product but insu?icient to cause‘ forma 15
tion of a solid polymerization product.
11. Ina process of producing liquid polymerization
products of an epihalogenohydrin of the formula
R1 and R3 indicate members selected from the group 25
consisting of hydrogen, lower alkyl, phenyl, cyclo
hexyl, and phenyl and cyclohexyl substituted by
2,581,464
Zech ________________ __ Jan. 8, 1952
2,706,189
Pruitt et al ____________ __ Apr. 12, 1955
2,712,000
Zech "-2. ___________ __ June 28, 1955
2,870,099
2,871,219‘
Borrows et al. ________ __ Jan. 20,
Baggett et a1. _________ __ Jan. 27,
Borkovec ____________ _.. Feb. 10,
Smith _______________ -_ June 16,
Gurgiolo et a1 _________ __ Nov. 3,
[Bailey _______________ __ Nov. 24,
Bresler et a1. _________ __ Dec. 15,
2,873,258
2,891,073
2,911,377
2,914,491
2,917,470
2,934,505
2,951,854
2,987,489‘
3,004,996
sisting of chlorine, bromine, and iodine,
said polymerization products having a terminal epoxy
1959
1959
1959
1959
1959
1959
1959
Gurgiolo ____________ __ Apr. 26, 1960
Chiddix et' al. _________ _. Sept. 6, 1960
Bailey et al. __________ __ June 6, 1961
Arakelian'et al ________ -_ Oct. 17, 1961
FOREIGN‘ PATENTS
lower alkyl, and
X indicates a halogen selected from the group con
Groll et a1. ___________ __ Jan. 25, 1938
Ballard et al __________ __ Feb. 21, 1950
30
477,843
751,244
966,389
199,877
Great Britain _________ .._ Ian. 3,
Great Britain _________ .. June 27,
France ______________ __ Mar. 1,
Austria _____________ .. Sept. 25,
1938
1956
1950
1958
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