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Патент USA US3079375

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3,0793%
Patented Feb. 26, was
1
2
the development of new polymeric plastic products, there
3,079,366
is a continued need for new ultraviolet absorbing ma
ULTRAVIOLET ABSQRBERS
terials which may be applied as ultraviolet absorbers to
American Cyanamid Company, New York, N.Y., a cor
poration of Maine
new class of ultraviolet absorbing materials as de?ned
SUBSTITUTED ARYLAMINOETHYLENES AS
Richard J. Boyle, Neshanic, Peter V. Susi, Middlesex, and 5 meet the requirements in various kinds of plastics.
The present invention is based on the discovery of a
Jerry P. Milionis, Bound Brook, N.J., asstgnors to
above. These compounds show useful ultraviolet ab
sorbing properties in a wide variety of organic substrates,
No Drawing. Filed June 26, 1961, Ser. No. 119,298
13 Claims. (Cl. 260-453)
This invention relates to a new class of ultraviolet ab
sorbing compounds and more particularly to substituted
arylaminoethylene ultraviolet absorbers represented by
the formula:
particularly polymeric plastic compositions, generally
10 with good ultraviolet light absorbing properties with su
perior light stability and lack of visible color (little or
no absorption in the visible range).
The compounds of the invention may be used in organic
carriers for stabilization of the carrier per se against the
15 effects of ultraviolet light, especially in polymeric com
positions such as polystyrene, polyesters, polyole?ns
(polyethylene, polypropylene, polybutylene and mixtures
thereof) polyvinyl chloride, polyvinyl acetate, poly(vinyl
(1')
chloride-acetate) poly(vinylchloride-vinylidine chloride)
wherein Ar is a carbocyclic aromatic radical of less than 20 polyvinyl ?uoride, poly(vinyl ?uoride-acetate), polyacry
three 6-membered rings which may be substituted by
lates, cellulosics (cellulose acetate, cellulose acetate-buty
hydroxy, alkyl, i.e., alkyl radicals of less than eighteen
carbons, alkoxy, halogen (especially those having an
atomic weight between 34 and 81) carboxy, carbalkoxy,
nitro, amino, monalkylamino and dialkylamino (espe
late, nitrocellulose), polycarbonate, polyoxymethylene,
25
cially alkyl of less than eighteen carbons) sul-fo (or alkali
metal salts) and/ or sulfonamido radicals; R is hydrogen,
alkyl of less than eighteen carbon atoms, cyanoalkyl
(especially wherein the alkyl group is of less than four
carbon atoms, e.g. cyanoethyl), aryl (especially mono 30
cyclic aryl, e.g. the phenyl radical which may bear any
of the substituents suitable for Ar); and aralkyl radicals
polyamides, alkyds (long-oil modi?ed; styrenated), poly
urethanes, polyureas, polyvinyl butyral, styrene-acrylo
nitrile, styrene-butadiene, styrene-butadiene-acrylonitrile,
acrylonitrile-vinyl acetate, phenol-formaldehyde, urea
formaldehyde, and melamine-formaldehyde. 'Ihe sta
bilized carriers may be used as screening for the protec
tion of other ultraviolet light-sensitive materials.
They are especially useful in polystyrene and in super
polyamides such as nylon and in polyole?ns such as poly
ethylene and polypropylene. Generally they are used
(especially monocyclic and lower alkyl e.g. benzyl and
in concentrations of from about 0.05 to 10.0% with a
phenethyl) R1 is hydrogen, lower alkyl, aryl radicals 35 concentration of about 0.2 to 1.0% being preferred for
(especially monocyclic aryl radicals which may bear any
practical results from the economic and functional stand
points.
They may be incomporated into the polymeric formula
of the substituents suitable for Ar) and aralkyl radicals
(especially monocyclic lower alkyl radicals, e.g. benzyl
and phenethyl) ; and X and Y are each cyano, carbalkoxy,
alkanoyl (especially lower alkanoyl, e.g. acetyl), aroyl
(especially monocyclic aroyl which may bear any of the
substituents suitable for Ar, e.g., benzoyl), carboxamido
40
or mono- or di-lower alkyl carboxamido. A preferred
class of compounds within the scope of Formula I is the
tions by the usual methods known in the art for this
purpose.
The compounds represented by Formula I are con
veniently prepared by conventional methods which may
be described brie?y as follows:
1. Reaction of an organic amine (such as aniline) with
alkyl esters of B-(N-methylanilino)-u-cyanoacrylate. 45 a lower alkyl orthocarboxylate (e.g. orthoforma-te, ortho
Another class of compounds within the scope of Formula
I of particular value in the stabilization of polyole?ns
is the l8-(N-alkylanilino)-a-cyanoacrylonitrile.
Various types of compounds have been used as ultra
acet-ate and orthobenzoate) and an appropriately substi
tuted active methylene group compound such as a malonic
acid derivative with or without a solvent, which reaction
may be exempli?ed by the following Equation 1:
violet absorbers for the protection of organic materials, 50
especially polymeric plastic compositions, against the
deteriorative action of ultraviolet light. To be effective
for such purposes, the compound used should have cer
tain characteristics such as the ability to absorb strongly
in the ultraviolet range, high stability to light of various 55
wave lengths both visual and ultraviolet, little or no ‘ab
sorption in the visible range (above 400 millimicrons),
low volatility, and compatibility with, and solubility in,
various types of organic carriers, etc. Although many
(2) Reaction of an aromatic amine such as aniline
with the appropriately substituted alkoxyalkylene-malono
derivative with or without a solvent which reaction may
be exempli?ed by the following Equation 2:
of the compounds used, meet the necessary requirements 60
in some respects, for some uses and in certain organic
substrates, few compounds can simultaneously ful?ll all
requirements. Many of the compounds, also, are de
?cient and unsatisfactory for some purposes. Thus, es 65
pecially with the development of new polymers, and with
+ ROH
Y
wherein Ar, R, R1, X and Y are as hereinbefore de?ned.
8,079,366
r
.
s
i
3
p-Anisidine
p-Chloroani-line
p-Butoxyaniline
p~Octadecyloxyaniline
o-Toluidine
2,4-dimethylaniline
2,4-dichloroaniline
m-Toluidine
p-Butylaniline
p-Dodecylaniline
N-methylaniline
N-cyanoethylaniline
N-octylaniline
102° C.
l-naph-thylamine
When 0.50% of ethyl u-cyanobeta-(N-methylanilino)
Octyl p-a-minobenzoate
m-Fluoroaniline
acrylate in polyoxymethylene was milled on a heated two
roll mill and then pressed into ?lm, the resulting ?lm
showed better light stability than the control without an
added U.V. absorber.
p-Bromoaniline
p-Aminobenzoic
p-Aminobenzenesulfonic
EXAMPLE 3.--ETHYL oc~CARBETHOXY-[3
acid
p-Aminophenol
N-propyl-p-aminophenol
2,4-dimethoxyaniline
4-aminosalicylic'acid
N-methyl-p-anisidine
o-Amino-phenol
ANILINOACRYLATE
A mixture of 4.7 g. of aniline and 10.8 g. of diethyl
ethoxymethylenemalonate is heated on the steam bath
for several hours. After cooling, a solid material crys
tallized out and the crude solid material was removed by
?ltration and recrystallized from petroleum ether, giving
Examples of the ‘active methylene group-containing
a product having a melting point of 50 to 51° C.
compounds which may be used in the reaction of Equa
EXAMPLE 4
20
tion 1 are:
Malononitrile
4
rated was isolated by ?ltration, washed with diethyl ether
and dried. The product weighed 224 g. (49% yield)
and after puri?cation from alcohol melted at 101 to
Examples of the aromatic amines which may be used
in these preparations are:
N-butyl-p-anisidine
Aniline
A variety of compounds was prepared using the'meth
Octyl cyanoacetate
Ethyl cyanoacetate
Diethyl malonate
Cyanoacetamide
N-octyl cyanoacetamide
Ethyl acetoacetate
Dibenzoylmethane
2,4-pentandione
Benz-oylacetonitrile
ods described in Examples 1, 2 and 3.
_
Thus, several series of derivatives were prepared fall'
25 ing within the scope of compounds as de?ned above de
rived from malononit-rile, diethylmalonate, ethyl cyano
acetate and benzoylacetonitrile, ethyl acetoace’tate, etc.
with variously substituted ‘aromatic amines of the ben
Methyl benzoyl acetate
Examples of the alkoxy alkylenemalono derivatives
zene and naphthalene series.
which may be used according to the reaction represented 30
in Equation 2 are those products derived from the reac
tion of trialkyl orthocarboxylate with the active methylene
group containing compounds listed above.
A useful method for the evaluation of the compounds
of the invention as ultraviolet absorbers involves deter
mination of the maximum absorption in the ultraviolet
range, determination of the absorbancy index of the com
pound at the maximum absorption which is an index of
The compounds prepared are listed in the tables shown
below.
.
'The compounds were evaluated as ultraviolet absorb
ers in a number of ways. Thus, the wave length of
maximum absorption in the ultraviolet range was deter
mined; the absorbancy index, which is a measure or index
of the degree of absorption, was determined usually at
the wave length of maximum absorption; and the extinc
tion coef?cient at the wave length of maximum absorp
the degree of absorption of the compounds and the ex
tion was also determined. The method used and the re
tint/tion coe?icient (epsilon) at the wave length of maxi 40 sults are shown below in the tables.
mum absorption.
Absorbancy Index
In addition since the stability to the action of light is
highly important for use of ultraviolet absorbing materials
For evaluation of compounds as ultraviolet absorbers,
for practical purposes, determination of vlight stability is
the wave length of maximum absorption in solvents such
a useful method for evaluating compounds. This may
be done by exposing the compound in solution to ultra‘ 45 as butyl acetate and toluene which are reasonable proto
types of oxygenated polymers and hydrocarbon polymers
violet light and then measuring the amount remaining as
was determined. The position of (the maximum wave
the original ‘compound after the exposure.
length of absorption is an ‘important factor in determin
The invention is further illustrated by the following
examples.
EXAMPLE 1 .-a-CYANO-,s- (p-M ETHOXYANI
ing whether a compound is suitable as an ultraxiolet ab
50 sorber.
In addition, the strength or degree of absorp
tion, especially at the wave length of maximum absorp
LINO ) ACRYLONITRILE
tion, is also useful in determining the e?iciency of an
ultraviolet absorber. A useful means for expressing the
To 250 ml. of ethanol was added 24.6 g. of p-meth
strength or degree of absorption is as the absorbency in
oxyaniline, 29.6 g. of triethyl orthoformate, and 13.2 g.
of lmalononitrile to form a solution which was heated 55 dex (absorption coef?cient).
For such measurements ultraviolet absorption curves
at there?ux temperature for three ‘hours. After vcooling,
are determined spectrophotometrically in an ultraviolet
the solid material which separated was isolated by ?ltra
spectrophotometer ‘on the compound in solution. The
tion, ?ushed with ethanol and recrystallized from a mix
absorbancy index at the wave length of maximum absorp
ture of acetone and ethanol giving 28.5 g. of product
with a melting point of 254'to 255° C.
, 60 tion desingated as amax is an expression of the degree of
absorption at the wave length of maximum absorption
EXAMPLE 2.—ETHYL aiCYANO-?-(N-M'ETH'YL
ANILINO)ACRYLATE
and; is calculated using the following relationship:
A mixture of 214 g. of N-methylaniline, 296 g. of
triethyl vorthoform'ate, and 226 'g. of ethyl "cyanoacet‘ate 65
a: —-
was stirred and heated at there?ux temperature until ‘the
temperature of the reaction mixture reached 165° C. The
apparatus in which this was ‘carried out was ?tted for
distillation after reaching 165° C., then mixture was
1 log
be
To
-—
‘where
heated at this temperature for an additional period (about 70
a is the absorption coe?icient
a half hour). (During this total period, approximately
b is the thickness of the spectrophotometer cell in centi
320 ml. of distillate resulted.)
'
The reaction mixture was then diluted with 500 ml. of
ethanol and after clarifying hot with activated charcoal,
meters
2: is the concentration in grams per liter
the solution was cooled; the solid material which sepa 75 T1 is the amount of light passing through solution
3,070,3ee
7
8
before the'sample ruptures is determined. The results are
TABLE v
expressed as follows:
Miscellaneous
.01.,
Am“
am“
(mu)
7
~
Ema“
Concentration
Percent
carbonyl
Percent
elongation
.
l
coon;
®NH~0H=C
ass
01
24, 200
COOCzHs
10
v
Control (no additive, not exposed) ______________________ __
726
8 .8
Control (additive, not exposed) _____ ._
-___ __________ ._
Control (no additive, exposed)-.."
__._
0.31
10.1% compound __________________ __
____
0. 23
105
0.5% compound _____________________________ __
0.06
568
38
ON
K
/
,
l\II—-CH=C\
_
om
305
118'
oooorn
1
CN
/
.
-—lTI-CH=C\
OH:
s05
81
ON
_
—NH——(l3=C\
CH3
}
>EXAMPLE'6
a-Cyano~?-anilino-acrylonitrile was applied to nylon
15 ta?eta fabric by an exhaustion method at 5% concentra
tion on the weight of the fabric. The exhaustion was
carried out using a 30:1 liquor to cloth ratio. The bath
was prepared with water only and the ‘fabric entered.
The temperature was raised slowly to the boiling point
00, 18,100 20 with constant stining and the ultraviolet absorbing ma
terial in ethanol solution was then gradually added.
When the addition of the ultraviolet absorber was com
-
/co0o2rr.
CH;
.
‘202
CN
®—NH—?=C\
'
plete, the exhaustion application was continued for an
I
other 60-minute period at the boiling point with continu
‘302' '01 21,000
CN
.
011.0-
25,300
000081111
/
_
~25,500
"
The 'fabric was then removed, rinsed
thoroughly and dried. The tensile strength loss in the
/
*
-'Nn-c|:=o\
on.
ous stirring.
I 0N
fabric was then determined after exposure "of the fabric
for 80 hours in a FadeOmeter and a Weather-Ometer (no
water spray in the Weather-Ometer). The results were
a
200
82
UN
17, 400
'
30 as follows:
/o00oz115
CH3O—®‘NH—(|)=O\
CH3
I
300. ' 81. 21,100
Tensile strength loss
CN
(percent)
35
WeatherOmeter
exposure
EXAMPLE 5
Films of polyethylene containing 0.1% and 0.5% of
a-cyano-B-(4-dodecylanilino)aerylonitrile were prepared
40
Untreated fabric ____________________________ __
Treated fabric _______________________________ .-
"Fade
Ometer
exposure
83
51
85
67
and the percent carbonyl formation on exposure to out
door weathering (including sunlight with ultraviolet) was
determined, in addition‘ to percent elongation.
Nylon taffeta fabric is protected against ultraviolet de
gradation by use of ethyl tx-cyano-beta-(N-phenylanilino)
The carbonyl group concentration after exposure is a
acrylate in a manner described in Example 6. Also use
direct index of the oxidative deterioration which has taken 45 ful in this application are ethyl a-cyano-beta-anilinocinna
place in the polyethylene under exposure to ultraviolet
light in daylight. A low relative concentration ‘of car
mate and N-ethyl weyanobeta-anilinoacrylamide.
EXAMPLE 7
bonyl in polyethylene containing the ultraviolet ‘absorber
To 100 grams of polystyrene, 0.25 gram ‘of ethyl a
‘after exposure shows protection against the effects of :50
cyano-?-(N-methylanilino)-acrylate were added on a hot
ultraviolet light. The elongation test as percent is a meas
‘two roll mill. One roll was maintained at 350° F. and
ure of how much the composition maybe stretched before
the other at 250° F. The mix was blended continuously
rupturing and shows the eliects of deteriorative action by
over a ten minute period by repeatedly passing the vmix
exposure to ultraviolet light.
through the nip of the rolls ‘for 70 passes. A small sam
The procedure used is described as follows. The ultra
violet absorber to be tested (either 0.1% or 0.5% concen
tration based on the polyethylene) and 100 g. of poly
ethylene (DYNH from Bakelite) are milled together for
40 passes (about 5 minutes) on-a-t-wo roll-mill which has
‘only the rear roll heated (about 330° F.). The milled 00
samples are next hot pressed between polished plates at
ple of this .mix was then compression molded into a
.050" x 2" x 2” chip. A yellow index reading was taken
before and after each designated exposure period in the
Fade-Ometer. The yellow index readings were deter!
mined according to ASTM D791-54.
about 325° F. into sheets vof about 0.010 to 0.015 in.
thickness (about 10 to 15 mils). Small pieces of these
‘sheets are then used for the test. For determination of
carbonyl content, small pieces of the sheets are mounted 65
.into holders and exposed outdoors at a 45° angle to the
horizontal and facing south. After exposure the infra red
spectra are determined for each sample in the range of 5
‘to -7 microns on an infra red spectrophotometenlthe ab .70
sorption at 5.8 microns being measured. The results may
be expressed in percent carbonyl.
-
Percent'elongation measurements of‘exposed and non
exposed samples are taken on an Instron Testing Machine.
Poly\ styrene,
grams
Ethyl ozcyano-‘B-
Yellow index
after “2;” hrs. in Fade-Ometer
(N -methyl
aniline)
acrylate,
grams
0 hr.
200 hr. 400 hr. 500 hr. 700 hr.
100
0
5. 9
11.8
23. 8
32.0 I
43. G
100
0.25
7. 1
8.1
10. 2
12.9
17. 4
_
Good protection ‘against ‘U.V. degradation is achieved
when ethyl u-cyano-beta-(N-cyanoethylanilino)-acrylate
is used in place of ethyl a-cyano-beta-.(N-methylanilino)
Thepercent elongation which. takes place .on stretching 7,5 .acrylate inExample 7..
8,079,366
9
EXAMPLE 8
The following formulation was compounded for ?ve
spacing). The mold was placed in an 80° C. oven for
30 minutes. The cured sheet was then exposed to an RS
sunlamp at 8" lamp to sample distance.
minutes in a heated two roll mill with the front roll at
350° F. and the rear roll at 250° F.
Parts
Yellow index I
iPolyvinylchloride (Bakelite VYNS) ____________ __ 85
'Polyvinylchloride (Bakelite VYHH) ___________ __ 15
Cadmium-barium soap (Argus, Mark 99) ______ __ 3
Stearic acid
0.5
U.V.
0.2
absorber1 ____________________________ ._
0
15
19
37
106
hrs
hrs.
hrs.
hrs.
hrs.
.... .
Control _____________________________ ._
4
21
24
24
25% aacyano-beta-anilino-acrylonitrile
4
7
8
13
18
1 Ethyl a-cyano-B- ( N -methylanilino) acrylate.
1 The formula used to calculate yellow index is as follows .
From this stock a 21 mil thick ?lm was compression
molded at 350° F. This ?lm was then exposed in the 15
Percent Russian-Percent R-llwmu
Yellow index- ——————————-———1.57><Pement
Rmmu
X100
Fade-Ometer and Weathcr-Ometer for the indicated
periods.
We claim:
1. A composition of matter resistant to the deteriora
tive effects of ultraviolet light comprising a polymeric ma
20 terial and from about 0.05% to about 10% by weight of
a compound represented by the formula
Yellow index
Unexposed
WOM
FOM
(100 hrs.)
(200 hrs.)
Control _________________________ _.
6
33
17
acrylate ______________________ _-
6
6
10
Ethyl a-eyano-?-rnethylanilino
25
where-in Ar is an aryl radical; R is a member selected from
the group consisting of hydrogen, alkyl, cyanoalkyl and
aryl; R1 is a member selected from the group consisting
The yellow index is determined on a differential colorime
ter using the following formula:
of hydrogen, lower alkyl, aryl and aralkyl; and X and Y
30 are each selected from the group consisting of cyano,
carbalkoxy, alkanoyl, aroyl, carboxamido and lower alkyl
Yellow index = 70 ( 100 —
carboxamido each of said aryl radicals having less than
Blue )
three G-membered carbocyclic rings, bearing substituents
Green
selected from the group consisting of hydrogen, hydroxy,
alkyl, alkoxy, nitro, halogen, carboxy, amino, alkylamino,
EXAMPLE 9
carbalkoxy, sulfo and sulfonamido radicals.
2. The composition of claim 1 wherein the polymeric
Into polypropylene was milled the following two U.V.
material is a polystyrene.
absorbers. The U.V. absorber was dry blended with the
3. The composition of claim 1 wherein the polymeric
powdery polypropylene for three hours. This mix was
then ?uxed for ?ve minutes on a heated two roll mill with 40 material is a polyoxymethylene.
4. The composition of claim 1 wherein the polymeric
the front roll at 350° F. and the rear roll at 320° F.
material is a vinylchloride polymer.
After this a 12 mil ?lm was compression molded from
5. The composition of claim 1 wherein the polymeric
this stock. This ?lm was exposed in the Fade-Ometer
material is a polyole?n.
and the exposure time at which the ?lm became brittle
45
6. The composition of claim 1 wherein the compound
was noted.
Brittle point
(hrs) FOM
Control
30
Ethyl a - cyano - beta - (N - methylanilino)
(0.25% )
70
100
EXAMPLE 10
'Into 4.5 parts of monomeric styrene were stirred 0.5
part of benzoyl peroxide and 0.25 part of a-cyano-beta
anilinoacrylonitrile.
polystyrene.
8. The composition of claim 6 wherein the polymer is
acylate
(0.25%)
_
_
oz - Cyano - beta - (p - dodecylanilino)acrylonitrile
is an alkyl ?-(N-methylanilino)-a-cyanoacrylate.
7. The composition of claim 6 wherein the polymer is a
This solution was then added to 95
a polyoxymethylene.
9. The composition of claim 6 wherein the polymer is a
polyole?n.
10. The composition of claim 1 wherein the compound
is an ethyl ,B-(N-methylanilino)-a-cyanoacrylate.
11. The composition of claim 10 wherein the polymer
is a polystyrene.
12. The composition of claim 1 wherein the compound
is 5(N-alkylanilino)-a-cyanoacrylonitrile.
parts of a polyester resin (i.e., Cyanamid Laminac Poly
13. The composition of claim 12 wherein the polymeric
ester Resin 4123). This total solution was poured into 60 material is a polyole?n.
a %" thick mold (two glass plates with gasket for Ms"
No references cited.
UNlTED STATES PATENT OFFICE
esTmeATE or QRREC'H
Patent No, 3,079,366
February 26; 1963
Richard J. Boyle et al.
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
-
C'olumn 27 line 37,, for "incomporated" read -~ incorporated
“=5 line 43‘, for ula‘" read -=¢=>(l) -~-=-; column 4,, line 60“ for
"’desingated" read -=~ designated =~~g column 5‘] lines 71 to 'ZllY
the formula should appear as shown below instead of as in the
patent:
»
CH3
1?]
CH3
column 8v line 8c in the table‘ under the heading "Percent
elongation“ second line thereofY for ""8! 8“ read -- 818 m»; ‘
column 9g lines 31 to 35g the formula should appear as shown
below instead
of
as
in the patent:
Y
'
Blue
Yellow indeXZYO 6» Green
Signed and sealed this lst day of December 19649
(SEAL)
Attest:
ERNEST W. SWIDER
Attesting Officer
’
'
EDWARD J. BRENNER
’ Commissioner of Patents
UNITED STATES PATENT OFFICE
I.
CERTIFICATE OF CORRECTION
Patent No, 39079366
February 7 26V 1963
Richard J. Boyle et a1.
It is hereby certified that error appears in the above numbered pat-v
ent requiring correction and that the said Letters Patent should read as
corrected
below.
.
.
.
Column 2g line 37,1 for "incomporated" read M- incorporated
M»; line 4.3" for "lg" read -==»(l) we; column 4,, line 6O‘7 for
E"desingated" read ~=~= designated =~g column 5v lines 71 to 74,,
the formula should appear as shown below instead of as in the
patent:
»
'
0H3
H3
column 8U line 8‘, in the table1 under the heading "Percent
elongation“ second line thereofY for "8! 8" read me 818 Fm;
column 9g lines 31 to 35? the formula should appear as shown
below instead of as in the patent:
"
Blue
Yellow
indexz7O
le-
>
'
'
»
Green
Signed and sealed this’ 1st day of December 1964‘, _ v -
(SEAL)
Attest:
ERNEST w. SWIDER.
Attesting Officer
’
’
' ‘
EDWARD J, BRENNER
V > f Commissioner of Patents
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