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Патент USA US3038897

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lhdddfig'l
‘Patented June 12, 1962
rates
2
unsaturated esters represented by the above Formulas I
and 11. Another object is to provide useful thermoplastic
polymers of the same. Another object is to provide poly
1
3,6383%’!
NORCAMYPHANYL
ESTERS OF a,B-UNSATU
D'LCARBQXYLTC AClllvd AND ?®LY
meric materials that have utility as oil additives, as ?lm
THEREUF
llohnME‘RS
R. Qaldwell,
Winston It. .lacirson, In, and Edward
Ul
H. Hill, ldingspurt, TG‘SHL, assignors to Eastman
Kodak Company, Rochester, N.Y., a corpnration of
NewDrawing.
lersey Filed Mar. 12, 1959, Ser. No. 798,518’
No
6 Claims. (Cl. 269-435)
This invention relates to norcamphanyl esters of 0:,5
and ?ber-forming materials and as molding compositions.
Another object is to provide processes for the preparation
of the monomers and polymers thereof. Other objects
will become apparent hereinafter.
In accordance with the invention, we prepare our new
monomeric compounds by refluxing one molecular pro
portion of a dicarboxylic acid such as maleic acid, fumaric
acid, itaconic acid, maleic anhydride, etc. with at least
monoethylenically unsaturated aliphatic dicarboxylic
acids, ‘and more particularly to such esters of maleic,
fumaric and itaconic acids, to polymers thereof, and to
the preparation of the same.
It is known that unsaturated bicyclic alcohols such as
two molecular proportions of a hydroxycamphanyl com
pound represented by the general formula:
2,5-endomethylene A3 tetrahydrobenzyl alcohol can be
condensed with mdunsaturated dicarboxylic acids to give
esters containing several ethylenic linkages which on poly
wherein n, R and R1 are as previously de?ned, in an inert
merization give thermosetting resins. Accordingly, such
hydrocarbon medium such as benzene, toluene, xylene,
resins have but limited utility. We have now found that
etc., in the presence of an acidic catalyst such as sulfuric
or toluenesulfonic acids. The water formed in the re
action is removed, for example, as the benzene azeotrope
and collected in a Dean-Stark trap. The reaction is com
pleted when no more
excess
by employing a saturated bicyclic alcohol, for example,
norcamphanyl alcohols with and-unsaturated dicarboxylic
acids, the resulting esters contain but a single ethylenic
linkage and are readily polymerizable to thermoplastic
‘of the alcohol is advantageously employed to ensure com
pletion of the reaction. Esteri?cation can also be carried
out by heating the acid or anhydride, the alcohol (in ex
represented by the following general formulas:
30 cess) and the acidic catalyst for several hours at 150° C
1
H
H
in an autoclave. However, the previously described meth
C R,
o
0
Rt 0
od employing benzene as the reaction medium is preferred
/
\I
H
H
I
~\
R-CH
C——(GHQ) “O C CHI-‘CH6 0 (CH2) "-0
CH~R
resins having a wide variety of uses.
The new class of unsaturated esters of the invention are
CH2 \
R-Cl-l \
\ /
\
CH1
l'lzC
o
H
primarily because higher yields are obtained and less
CH2 1
\
\ /
GH—R
0 alcohol is required.
The polymerizations for preparing the resinous thermo
plastic polymers of the invention may be carried out con
G
H
veniently in an organic solvent such as one of the lower
alcohols, ketones or esters or in a hydrocarbon such as
benzene, toluene or hexane. Mass or bulk polymeriza
and
11
r
H
Isl/x
l GEL-R
cfoom?nro\
H2O
l
CH2 \
\
\ /
40 tions may also be used. The polymerizations can also be
carried out by dispersing the monomers in water and add
CH-—-R
ing suitable dispersing agents. Catalysts, beat and actinic
G
light accelerate the reactions. Suitable catalysts that can
be used alone or in admixture include peroxides such as
H
IT.
\
0
R1 C
\\ I
C ——'CH (X0112) n-Cl
OH: CH—R
Hac \ CH-—R
45
/
benzoyl peroxide, acetyl peroxide, lauroyl peroxide, ter
tiary butyl hydroperoxide, hydrogen peroxide, etc, per
sulfates such as sodium, potassium and ammonium per
sulfates, perborates such as sodium and potassium per
a methyl group. These monomers are useful as chemical
borates, etc. AZobis-isobutyronitrile may also be em
ployed as a catalyst. The amount of catalyst used can
‘vary from about 0.1 to 3.0%, based on the Weight of
monomer to be polymerized. The temperature can vary
over a wide range e.g. from 20°~l30° 'C., but preferably
the polymerizations are carried out at ‘from about 50°
55 70“ C. The polymerizations can be carried out by batch
or continuous processes at atmospheric or higher pres
intermediates for the preparation of various derivatives
can be maintained in the reaction vessel. When carried
c
H
wherein n represents an integer of O or 1, each R repre
sents the same member such as an atom of hydrogen or '
an alkyl group of 14 carbons such as methyl, ethyl,
propyl, isopropyl, butyl, etc. groups, and each R1 repre
sents the same member such as an atom of hydrogen or
thereof and are especially valuable as intermediates for
preparing resinous thermoplastic polymers that are useful
for the manufacture of films, ?bers, sheets, tubes, molded
obiects and as oil additives. Such resinous thermoplastic
polymers are soluble in common organic solvents such as
sures. If desired, an inert atmosphere such as nitrogen
out in a nonsolvent medium such as water, an activating
60 agent such as an alkali metal bisul?te e.g. sodium or po
tassium bisul?te may advantageously be employed. Also,
it is advantageous in an aqueous system to employ surface
active agents such as fatty alcohol sulfates e.g. sodium or
carbon tetrachloride, chloroform, benzene, toluene, min
cetyl sulfate, sodium or potassium lauryl sul
eral oils, tertiary butyl alcohol, higher esters of phthalic 65 potassium
fate,
etc.,
aromatic sulfonates eg sodium or potassium
acid, etc., but insoluble in solvents such as water, acetone,
salts of alkylnaphthalene sulfonic acid, sulfonated oils,
methanol, acetonitrile, cellosolve, and the like. They
and the like. These surface active agents may be em
vary from soft gums represented by the homopolymers to
ployed up to about 3-5% of the weight of the monomer
materials having melting points up to about 250° C. rep
be polymerized. If desired, a chain regulator such as
resented by various copolymers which on molding give 70 to
an alkyl mercaptan e.g. hexyl, cetyl, lauryl, myristyl, etc.
clear, hard molded objects or ?exible, tough ?lms, ?bers
mercaptans, can be employed.
andIt sheets.
is, accordingly, an object of the invention to provide
.>
-
~
3,038,887
:,
was re?uxed for 13 hours.
a Dean-Stark trap attached
After the reaction mixture was worked up as in Example
1, the product was recrystallized
give 290 g. (87% ‘
80°—82° C, of bis(2-norcarnphanylmethyl) fumarate
proportions can be employed,
are from 10-90%
represented by the following structural formula:
'
the invention
'
by weight
Hcooocm/I
/I ~om0oiicn
L9
10
In general, the resulting co
he//
I/
15
ethyl,
Bis(2—norcamphanyl) maleate was prepared from ma
leic acid and Z-norcamphanol according to the procedure
of
Example 1.
is ester was a colorless liquid, B.P.
l95~l98 ° C./2 mm.
20
EXAMPLE 4
Bis(2-norcamphanylmethyl) maleate was prepared
‘ anhydride and Z-norcamphanemethanol ac~
Example 1. This ester was
25 a colorless liquid, B.P. 206°—209° C./3 mm.;
"D20 1.5073
EXAMPLE 5
.Bis(2-methyl-2-norcamphanyl) maleate was prepared
from maleic anhydride and Z-methyI-Z-norcamphanol ac
'
procedure of Example 1.
stilled at 202°-206° C./2 mm.
This ester dis
EXAMPLE 6
methylstyrene, p-acetaminostyrene, etc., vinyl
idene halides e.g. vinyl chloride, vinyl ?uoride, vinyli
dene chloride, vinylidene ?uoride, etc., tetra?uoroethyl
Bis(2,3~dimethyl~2-norcamphanylmethyl) maleate was
35
prepared from maleic anhydride and 2,3-dimethyl-2-nor
ene, chloro-tri?uoroethylene, N-vinyl imides such as N
vinyl succinimide, N-vinyl phthalimide, etc., N-vinyl lac
tams e.g. N-v-inyl pyrrolidone,
-vinyl piperidone, etc.,
a-ole?ns containing from 2-8 carbon atoms e.g. ethylene, 40
mg to the procedure of Example 2
at 204 °—206° C./3 mm.
This ester distilled
EXAMPLE 8
A mixture of 25 g. of bis(2-norcamphanylmethyl)
The following examples will serve to illustrate further
the new monomers, polymers thereof and the manner of
their preparation and uses.
and 0.3
g. of
benzoyl peroxide .was tumbled in a pressure
bottle
at
°
for 12 h
22 g. of soft gum
identi?ed
In placeasofp
itaconate.
'
there may be substituted a like amount of any other of
?uxed for 48 hours.
55 the mentioned unsaturated esters of the invention to give
omopolymers of generally similar
'
reaction was collected
a short Vigreux column.
istics, for example, poly-bis(2-norcamphanyl) fumarate,
The benzene solution was
poly-bis(2-norcamphanyl) maleate, poly-bis-(Z-norcam
cooled, washed With sodium bicarbonate solution, dried
phanyl) itaconate, poly~bis(2-norcamphanylmethyl) fu
60 marate,
th e 11k‘e.
poly-bis(2-norcamphanylmethyl) maleate, and
EXAMPLE 9
A mixture of 16.5 g. (0.05 mole) of -bis(2-norcam
HO O O O
I
I _0 0 (5H
5
e
i/
l/
EXAMPLE 2
A mixture containing ‘116 g. (1.0 mole) of fumaric
acid, 258 g. (2.05 moles) of Z-norcamphanemethanol,
300 ml. of benzene and 10 g. of p-toluenesulfonic acid
65
phanylmethyl)fumarate,
(0.05 mole)
stearate, 150 ml. of tert.-butyl alcohol and 0.5 g.
acetonitrile several times.
70 91%. It consisted of approximately 51%
recurring units of the f
of thestearate
polymer
molecule being recurring units of the
vinyl
component.
The above polymer was tested as an
75 oil. The table below compares its additive in mineral
performance with
EXAMPLE 14
A mixture of 5 g. of bis(6-methyl-2-norcamphanyl)
mineral oil alone and with Acryloid 618 (a commercial
acrylic resin oil additive).
Table
Viscosity
stokesin centi
ASTM
slope
fumarate, 45 g. of methyl methacrylate, 300 ml. of
acetone and 0.5 g. of acetyl peroxide was tumbled in a
pressure bottle at 60° C. for 10 hours. The resulting co
polymer contained approximately 10% by weight of the
above fumarate component. It was isolated by evaporat
ing the solvent. A yield of 48.8 g. of copolyrner was ob
Viscosity
index
J/
2l0° C.
tained. It was thermoplastic and molded readily to give
10 clear, hard molded objects.
EXAMPLE 15
A mixture of 10 parts by weight of bis(2-nor
camphanylmethyl) fumarate and 90 parts by weight of
acrylonitrile was added slowly over a period of one hour
at 60° ‘C. to a stirred solution containing by weight 400
The ?rst column shows the difference in viscosity of the
oil at two di?erent temperatures, with and without the
parts water, 1 part of potassium persulfate, 0.5 part of
sodium bisuliite and 2 parts of lauryl alcohol sulfate.
At the end of 6 ‘hours, the copolymer containing approxi~
mately ‘10% by weight of the fumarate component was
isolated by pouring the emulsion into a 20% solution of
speci?ed additives. The second column is an indication
of the rate of change of the viscosity with temperature.
A small numerical value is desirable. The viscosity in
dex of the last column is an empirical number indicating
sodium sulfate, washed and dried. The yield was 97 g.
the effect of change of temperature on the viscosity of
of copolyrner. It had a softening point of approximate
an oil. A low viscosity index signi?es a relatively large
ly 225°~230° C. A dope of the copolymer in dimethyl
change of viscosity with temperature. Thus, it will be
formamide was wet-spun into fibers which after drafting
seen that the copolymer of above Example 6 improves 25 had a tenacity of 3.2 g./ denier and an elongation of 18%.
the mineral oil in every case, and in addition shows su
EXAMPLE 16
periority in producing and maintaining a relatively higher
viscosity over the temperature range of 100-210° C. than
shown by the comparison samples.
EXAMPLE 10
Using the method of preparation, puri?cation and oil
additive testing of Example 9, a gum-like copolyrner pre
A mixture of 25 g. of bis(2-norcamphanyl) fumarate,
75 g. of vinyl chloride, 400 ml. of tert.-butyl alcohol and
30
1.0 g. of benzoyl peroxide was tumbled in a pressure
bottle at 55° C. for 18 hours. The resulting copolyrner
was isolated by pouring the reaction mixture into aceto
nitrile, followed by ?ltering off the precipitate, washing
pared ‘from a mixture of 23.4 g. (0.075 mole) of bis
(2-norcamphanyl)fumarate, 15.5 g. (0.075 mole) of
and drying. A yield of 88 g. of white copolyrner was
obtained. It contained 79% of the vinyl chloride com
ponent as shown by chlorine analysis and was an excel
35
vinyl stearate, 200 ml. tert.-butyl alcohol and 0.5 g. of
benzoyl peroxide showed a viscosity value of 28.87 at
100° C. and 5.03 at 210° C., an ASTM slope of 0.73 and
‘a viscosity index of 112.1.
EXAMPLE 11
bis(2-norcamphanylmethyl) -
lent molding material.
EXAMPLE 17
40
A mixture of 90 g. of bis(2-norcamphanyl) fumarate,
10 g. of vinyl stearate, 500 ml. of tert.-butyl alcohol and
1.0 g. of aZo-bis-isobutyronitrile was tumbled in a pres
A mixture of 8 g. of 200 ml. of toluene and 0.4 g.
sure bottle at 60° C. for 24 hours. The copolyrner was
tumbled in a pressure
of aZo-bis-isobutyronitrile was
isolated by pouring into acetonitrile and puri?ed as de
bottle at 70° C. for 24 hours. A clear, viscous dope 45 scribed in above Example 9. It contained approximate
fumarate, 32g. of styrene,
was obtained which was poured into acetonitrile to pre
cipitate the polymer. After separation and drying, the
copolyrner product weighed 37.6 g. It consisted of ap
proximately 20% by weight of recurring units of bis(2
norcamphanylmethyl) fumarate, the remainder of the co
polymer molecule being recurring styrene units, and was
ly 90% by weight of the above fumarate component, the
remainder of the copolyrner molecule
the vinyl
stearate component. This product was readily soluble in
50
thermoplastic. On compression molding, the copolymer
gave clear, hard molded objects.
EXAMPLE 12
A mixture of 23.4 g. (0.075 mole) of bis(2-nor
camphanyl) maleate, 7.5 g. (0.075 mole) of isopropenyl
mineral oil and was useful as an oil additive.
EXAMPLE 18
A mixture of 20 g. of bis(6-methyl-2-norcamphanyl)
itaconate, 50 g. ‘of vinyl acetate, 200 ml. ‘of tert.-butyl
alcohol and 0.5 g. ‘of ibenzoyl peroxide was refluxed for
10 hours in a flask equipped w'th a reflux condenser.
The resulting copolymer was obtained by precipitating
the reaction mixture into methanol. A yield of 61 g. of
acetate, 100 ml. of tert.-butyl alcohol and 0.3 g. of ben
a soft gum was obtained. it contained approximately
zoyl peroxide was heated at re?ux in a 250-ml. ?ask for
28% by weight ‘of the above fumarate component and
A clear, viscous dope was obtained which was 60
was readily soluble in chloroform.
acetonitrile to precipitate the copolymer.
By proceeding as described in the above examples,
the copolymer product weighed 29.4 g. It
other
of the mentioned monomers and corresponding
After drying,
contained approximately 76% by weight of recurring
units of bis(2-norcamphanyl) maleate, the remainder of
the copolyrner molecule being recurring isopropenyl
polymers thereof can be prepared. Where the polymers
units, and was thermoplastic. It was useful primarily as
an additive to synthetic lubricants.
cases where
EXAMPLE , 13
A mixture of 5 g. of bis(2-norcamphanylmethyl)
maleate, 35 g. of vinyl acetate, 400 ml. of water, 0.4
persuliate, 0.2 g. of sodium bisul?te
> g. of ammonium
are gum-like in character, these are generally useful as
mineral oil additives and as plasticizing agents, and in
are solids as in the case of
certain copolyrners these are useful for preparing ?lms,
sheets and molded objects. The copolymers with acrylo~
nitrile containing at least 70% of the acrylonitrile com
ponent are particularly useful for the preparation of ?la
ments and ?bers. The polymers ‘of the invention can be
extruded from their melts or cast from solutions thereof
and 0.4 g. of sulfonated mineral oil was tumbled in a
in appropriate solvents. Those polymers giving flexible
pressure bottle at 55° C. for 20 hours. A milky emul
tough ?lms are also useful as photographic ?lm support
sion of copolymer was obtained from which clear, ?exi 75
ble ?lms were readily cast.
3,038,887
materials. Suitable ?llers, dyes, pigments, softening
agents,
etc. can be incorporated, if desired, into the copoly—
mer
compositions.
The invention has been described 'in detail
ticular reference
What we claim is:
on atoms, styrene,
1. A thermoplastic copolymer of from 10-90%
v1nyl chloride.
weight of an unsaturated ester selected from those
resented by the following general formulas:
H
H
/R' l )
l!) R‘\ /0
H2 l —(OHQ)DOCCH=CHCO(CHZ)D—C
15 versely from 90—10 0 lb
1/0
4 A thermoplastic copolymer of from 10~90%
weight of bis(‘6-methyl-2-norcamphanyl) fumarate and
conversely from 90-10% by weight of methyl meth
a'crylate.
20
5. A thermoplastic copolymer of from 10-90% by
weight of ibis(Z-norcamphanylmethyl) fumarate and con
Weight of bis(6-methyl-2-norcamphanyl) itaconate and
conversely from 9‘0~1*0% by Weight of vinyl acetate.
References Cited in the ?le of this patent
/l\
UNITED STATES PATENTS
30
35
2,098,190
2,366,495
2,683,126
2,744,098
Kyrides _____________ __ Nov.
D’Alelio ______________ __ Jan.
Nichols _______________ __ July
Towne _______________ __ May
2,
2,
6,
1,
1937
1945
1954
1956
2,892,858
Ziegler ______________ __ June 30, 1959
2,912,458
Brannock ____________ __ Nov. 10, 1959
2,926,806
Marvel et al. ______ __'___ Mar. 22, 1960‘
FOREIGN PATENTS
40
487,593
Great Britain _________ __ June 22, 1938
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