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Патент USA US3055864

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he
3,055,86l
Patented Sept. 25, 1962
l
2
3,055,861
novel and improved stabilizing materials which increase
the resistance of certain halogen-containing ole?n resins
STABILIZED ACRYLONITRILE VINYL 0R
DENE COPOLYMER SOLUTIONS
Ll
Solomon P. Hersh, Charleston, and George W. Fowler,
South Charleston, W. Va, assiguors to Union Carbide
Corporation, a corporation of New York
No Drawing. Filed Feb. 19, 1958, Ser. No. 716,039
4 Claims. (Cl. 260—45.7)
The present invention relates to stabilized resin com
positions prepared from halogen-containing ole?ns and
to discoloration upon exposure to heat or light.
Still
another object of the invention is to provide a novel
process for retarding or inhibiting the discoloration of
certain halogen-containing ole?n resins upon exposure to
heat or light. Other objects will become apparent in
light of the following description.
The present invention is particularly concerned with
10 the stabilization of halogen-containing vinyl resins of the
type prepared by .the conjoint polymerization of vinyl
to processes for producing such stabilized resin composi
tions. More particularly, the invention relates to new
and improved stabilizing materials which show de?nite
chloride or vinylidine chloride, or both, with acrylonitrile.
Within the broader class of these resins, conjointly polym
erized vinyl chloride or vinylidene chloride, or both,
advantage in increasing the resistance of halogen~con 15 with acrylonitr-ile, containing in the resin from about
15 percent to about 70 percent of the chlorine-containing
taining ole?n resins to discoloration.
monomer by Weight, are especially susceptible to sta~
Halogen-containing ole?n resins are well known to
bilization by the materials hereinafter described. In
the art and ?nd use in :a number of diverse applications.
cluded among the resin compositions contemplated by
Noteworthy among these uses is the role such resins play
in the production or manufacture of synthetic ?bers. It 20 the invention are solutions of these resins, such as those
in common usage as spinning “dopes” for the production
is also well known that resin compositions prepared from
of synthetic ?bers, wherein the resin is dissolved in a
halogen-containing ole?ns are sensitive to heat and light
suitable inert organic solvent, for example, acetonitrile,
as manifested by discoloration. Thus, for example, in
the production of synthetic ?bers from such resin com
acetone, the N,N-dialkyl formamidcs and acetamides,
positions, the resin is ordinarily dissolved in a suitable 25 ethylene carbonate, cyclohexanone, etc., or any other
inert organic solvent for the resin which will not react
organic solvent and maintained in solution at elevated
with the stabilizer employed or the resin itself.
temperatures for prolonged periods of time during the
spinning operation. During these procedures, the color
In accordance with the invention, it has been found
that certain trio-rgano-phosphorus compounds containing
of the hot res-in solution generally undergoes a progressive
yellowing or darkening which undesirably affects the 30 trivalent phosphorus will function as excellent stabilizers
for the resin compositions described herein. More par
initial color of the ?bers ultimately produced. Moreover,
ticularly, the triorgano-phosphorus compounds of this in
a continued gradual development of color in these ?bers
vention can be represented by the general formula:
usually can also be observed upon exposure to light, or
when the ?bers are subsequently subjected to high tem
x
perat-ures ‘as during the ironing or pressing of fabrics pre 35 (I)
pared from the ?bers.
While the initial stages of color development reached
during formation or subsequent treatment of the resin
compositions may not materially detract from some quali
wherein X, X1 and X2 each represents either a hydro
ties of the resin, they ‘frequently are suf?cient to restrict 40 carbyl radical, i.e., a radical containing only carbon and
many uses of the resin. Consequently, continued color
hydrogen atoms, such as alkyl, alkenyl, aryl, alkaryl,
development in the resin compositions becomes increas
aralkyl, cycloalkyl or cycloalkenyl radical, or a hydro
ingly undesirable. It is therefore customary to incor
carbyloxy radical corresponding thereto, such as an
porate in halogen-containing ole?n resin compositions
alkoxy, alkenoxy, aryloxy, alkaryloxy, aralkoxy, cyclo
small amounts of stabilizing materials for the purpose of
alkoxy, or cycloalkenoxy radical, and wherein when one
retarding or inhibiting discoloration.
or more of the radicals represented by either X, X1 or
Heretofore, a considerable number of compounds de
X2 are hydrocarbyloxy radicals, at least one such hydro
signed to function as stabilizers for this purpose have
carbyloxy radical contains an aliphatic carbon atom at
been proposed)’ for example, lead and calcium salts of the
tached to the oxygen atom of the hydrocarbyloxy radical
higher fatty acids, alcoholates of the alkaline earth metals,
connected to the phosphorus atom. In addition, the hy
mono- and dialkyl phosphites, tri-(Z-chloroethyl) phos
drocarbyl or hydrocarbyloxy radicals can ‘also be substi
phite, di- and triaryl phosphites, various organotin com
tuted by hydroxy, allcoxy, aryloxy, carbalkoxy or acyloxy
pounds such as dioctyltin maleate, etc. Unfortunately,
radicals. As hereinafter employed, the term “substituted”
however, many of these compounds have not been found
refers speci?cally to the inclusion of these latter radicals
entirely satisfactory in minimizing the discoloration of
as substituents on the hydrocarbyl or hydrocarbyloxy
halogen-containing ole?n resin compositions upon pro
nucleus.
longed exposure to the action of either elevated tempera
When incorporated in the halogen-containing vinyl
tures or light. This is particularly true when the resin is
resin compositions hereinabove described, these triorg-ano
in solution, as in the instance of spinning “dopes” used
60 phosphorus compounds are re?ective in substantially pre
for the production of synthetic ?bers.
venting the discoloration of the resin compositions upon
Accordingly, one or more of the following objects can
‘exposure to heat or light. In this manner, for example,
now be achieved through the practice of the present in
the discoloration of ?ber-spinning solutions prepared in
vention, thus overcoming disadvantages of the prior art.
accordance with the present invention can now be min
It is an object of this invention to provide halogen-con
Pia
\X2
taining ole?n resin compositions which show improved
imized during conventional spinning operations. In addi
resistance to discoloration upon exposure to heat or light.
tion, synthetic ?bers can be obtained from these solutions
having a good initial whiteness, i.e., low color, and which
demonstrate improved stability upon subsequent exposure
of resins prepared from halogen-containing ole?ns, and
articles produced therefrom, which evidence a minimized 70 to heat and light.
Included among the triorgano-phosphorus compounds
tendency toward discoloration upon exposure to heat or
found to be effective as stabilizer for the purposes of this
light, A further object of the invention is to provide
It is another object of the invention to provide solutions
3,055,861
3
4
invention are triorgano phosphites (II) represented by
phosphorus compounds are the 1,3,2-dioxaphospholanes
(VI) represented by the general formula:
the general formula:
(11)
/OR
P~OR1
0R3
wherein R, R1 and R2 each represents either an unsubsti
tuted or substituted hydrocarbyl radical, and wherein at
least one hydrocarbyl radical is attached to the oxygen 10 wherein X, X1, X2, X3 and X4 each represents either an
unsubstituted or substituted hydrocarbyl radical or an
atom by an aliphatic carbon atom, for example, unsubsti
unsubstituted or substituted hydrocarbyloxy radical as
twted and substituted alkyl, alkenyl, aryl, alkaryl, aralltyl,
cycloalkyl and cycloalkenyl radicals containing up to
hereinabove de?ned for X, X1 and X2, containing up to
about 22 carbon atoms and preferably up to about 12
about 22 carbon atoms and preferably up to about 12
cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, biphenyl,
naphthyl, methylphenyl, ethylphenyl, phenylethyl, phenyl
hexyl, cyclohexylphenyl, hydroxyethyl, hydroxydodecyl,
methoxyethyl, ethoxybutyl, phenoxyhexyl, carbethoxy
ethyl, propionoxyoctyl, benzoxyhexyl, etlroxybutenyl,
phenoxybutenyl, carbethoxyhexenyl, propionoxypentenyl,
mula:
(VII)
carbon atoms, such as, methyl, ethyl, butyl, pentyl, hexyl, 15 carbon atoms. Also included within the group of cyclic
triorgano-phosphorus compounds are the 1,3,2-dioxa~
ethylhexyl, isooctyl, decyl, dodecyl, hexadecyl, propenyl,
phosphorinanes (VII) represented by the general for
.methylpropenyl, butenyl, pentenyl, hexenyl, octadecenyl,
20
benzoxyhexenyl, hydroxyphenyl, methoxyphenyl, car
bethoxyphenyl radicals and the like. Particularly good 25
results can be obtained when the triorgano-phosphorus
wherein X, X1, X2, X3, X4, X5 and X6 each represents
either an unsubstituted or substituted hydrocarbyl radical
compound employed in this invention is a trialkyl phos
or an unsubstituted or substituted hydrocarbyloxy radical
phite.
as hereinabove de?ned for X, X1 and X2, containing up
Also included among the triorgano-phosphorus com
about 22 carbon ‘atoms and preferably up to about 12
pounds are the triorgano phosphonites (III) represented 30 to
carbon atoms. In these cyclic triorgano-phosphorus com
by the general formula:
pounds, at least two oxygen atoms connected to the phos
phorus atom are attached to aliphatic carbon atoms.
(III)
Illustrative of the triorgano-phosphorus compounds
OR2
35 suitable for use in the present invention are the following:
wherein R, R1 and R2 each represents either an unsubsti
tuted or substituted hydrocarbyl radical as de?ned above,
and wherein at least one of the hydrocarbyl radicals rep
resented by either R1 or R2 is attached to the oxygen 40
atom by an aliphatic carbon atom.
Another group of triorgano-phosphonls compounds
included Within the scope of the present invention are
the triorgano phosphonites (IV) represented by the gen
eral formula:
45
,(IV)
50
wherein R, R1 and R2 each represents either an unsubsti
tuted or substituted hydrocarbyl radical as de?ned above,
and wherein the hydrocarbyl radical represented by R2
_is attached to the oxygen atom by an aliphatic carbon
atom.
A further group of triorgano-phosphorus compounds
included within the scope of this invention are the tri
organo phosphines (V) represented by the general for
mula:
Triethyl phosphite,
Tributyl phosphite,
Triisobutyl phosphite,
Tripentyl phosphite,
Trihexyl phosphite,
Tri-(2-ethylhexyl) phosphite,
Triisooctyl phosphite,
Tridecyl phosphite,
Tridodecyl phosphite,
Diethyl butyl phosphite,
Tripropenyl phosphite,
Tri-(Z-methylpropenyl) phosphite,
Trioctadecenyl phosphite,
Dipropenyl butyl phosphite,
Dipropenyl phenyl phosphite,
Diphenyl ethyl phosphite,
Dibutyl phenyl phosphite,
Z-methylphenyl dibutyl phosphite,
Z-phenylethyl dihexyl phosphite,
' Tri-(8-hydroxyoctyl) phosphite,
Di-(2-hydroxyphenyl) butyl phosphite,
Tri-(2-ethoxyethyl) phosphite,
4-phenoxybutyl dibutyl phosphite,
'I‘ii-(2—phenoxyethyl) phosphite,
Tri- (Z-carboxyethyl) phosphite,
Tri-( 3-acetoxy propyl) phosphite,
/R
Z-methoxyphenyl dibutyl phosphite,
P-Rl
Tributyl phosphonite,
32
Dibutyl phenylphosphonite,
Tridodecyl
phosphonite,
wherein R, R1 and R2 each represents either an unsubsti
Didodecyl
phenylphosphonite,
tuted or substituted hydrocarbyl radical as de?ned above.
Dihexyl propenylphosphonite,
In this group of triorgano-phosphorus compounds, the
Tripropenyl phosphonite,
limitation as to an aliphatic carbon atom attached to an
Tri-(Z-methylpropenyl) phosphonite,
oxygen atom connected to a phosphorus ‘atom does not 70 Tri-(Z-hydroxyethyl) phosphonite,
apply, since in the triorgano phosphines, oxygen is not
Di-(Z-methoxyethyl) phenylphosphonite,
‘connected to phosphorus.
Dihexyl 2-ethoxyphenylphosphonite,
(V)
It is to be noted that the triorgano-phosphorus com
Tri- (6-carbethoxyhexyl) phosphonite,
pounds of this invention can also be cyclic in con?gura
Di-(4-acetoxybutyl) phenylphosphonite,
tion. Included within this group of cyclic triorgano 75 Trietyl phosphinite,
3,055,861
5
Trihexyl phosphin-ite,
Tridodecyl phosphinite,
Butyl dipropenylphosphinite,
Butyl .diphenylphosphinite,
Tripropenyl phosphinite,
usage as spinning “dopes’tfor the production of synthetic
?bers, the triorgano-phosphorus compounds are prefer
ably added to the resin solvent prior to the addition of
resin. However, the stabilizers can ‘also be added during
or following the dissolution of the resin in the solvent.
The stabilized resin solutions prepared in accordance
with the present invention evidence little if any discolora
Tri-( l-methylpr op enyl) phosphinite,
Z-methylpropenyl diphenylphosphinite,
tion during ?ber spinning operations, thus resulting in
the production of synthetic ?bers having a high degree
> Tri-(Z-hydroxyethyl) phosphinite,
6-methoxyhexyl diphenylphosphinite,
Tr-i-(Z-carbethoxyethyl) phosphinite,
4-acetoxybutyl diprop enylphosphinite,
Tributyl phosphine,
Trihexyl phosphine,
Tridodecyl phosphine,
Diethyl butyl phosphine,
Tripropenyl phosphine,
Tri-(Z-methylpropenyl) phosphine,
Triehxenyl phosphine,
'Ilrioctadecenyl phosphine,
Dipropenyl butyl phosphine,
Triphenyl phosphine,
Tri-(2,4~dimethylphenyl) phosphine,
Tri-(Z-phenylethyl) phosphine,
Dipheny-l hexy-l phosphine,
Dipropenyl phenyl phosphine,
Tri-(o-hydnoxyhexyl) phosphine,
'I‘ri~(2-methoxyethyl) phosphine,
Tri-(3-methoxyphenyl) phosphine,
Tri-(Z-carboxyethyl) phosphine,
Tri-(2-acetoxypropyl) phosphine,
4-phenoxyphenyl dimethyl phosphine,
4-methoxyphenyl dipropenyl phosphine,
2-ethyl-1,3,2-dioxaphospholane,
2apropenyl-1,3,2-dioxaphospholane,
2-pheny1-1,3,2-dioxaphosphoiane,
10 of initial whiteness and low color. ‘In addition, the pres
euce of the stabilizing materials in the ?bers so produced
thereby inhibits discoloration when the ?bers are subse
quently subjected to high temperatures or exposed to
light.
certain halogen-containing ole?n resins, is also substan
tially eliminated. The solubility of the triorgano-phos
phorus compounds in conventional solvents such "as aceto
nitrile, acetone, dimethyl 'formamide, etc. facilitates the
20 spinning operation :and avoids the necessity of working
with a two-phase spinning solution.
The utility and advantages of the stabilizers of this in
vention, as well as of the resin compositions stabilized
therewith, will further become apparent from the follow
25 ing examples included to illustrate the best modes of
practicing the invention that are now contemplated.
EXAMPLE I
A series of experiments was conducted to demonstrate
the stabilizing action of various triorgano-phosphorus
compounds. Each experiment was carried out as fol~
lows. One hundred ?fty grams of acetone were intro
duced to ‘a one-pint pressure bottle and cooled by placing
the bottle in an acetone-“Dry Ice” bath for about 30
minutes ‘or until the temperature of the acetone reached
‘approximately ~20“ C. One gram of the particular
stabilizer utilized in each experiment was subsequently
dissolved in the acetone, and to this cool solution, 50
grams of a copolymer of vinyl chloride (60 percent) and
Z-decyloxy-l,3,2-dioxaphospholane,
2-( Z-hydroxyethoxy ) -\l , 3 ,Z-dioxaphospholane,
2-phenoxy-4-methyl-l,3,2-dioxaphosphoiane,
2-phenoxy-4-methoxy-1,3,2-dioxaphospholane,
2- (Z-methoxyethyl) -5 -acetoxy- l ,3 ,2ddioxaphospholane,
Bleaching of the ?bers during early exposure
15 periods to light, heretofore frequently encountered with
40
acrylonitrile (40 percent), having a molecular weight
2~hexyl-4,5 ~diethyl- l ,3 ,Z-dioxaphospholane,
such that the speci?c viscosity of an 0.2 percent solution
2-phenoxy-4,4,6~trimethyl-1,3 ,Z-dioseaphosphorinane,
of the resin in cyclohexanone at a temperature of 20°
C. was 0.261 were ‘then added. The bottle containing the
solvent, stabilizer and resin was capped, enclosed in a
2-dodecyl-4-phenylethyl-l,3,2~dioxaphospholane,
Z-methoxy-S-ethyl-4~propylnl,3,2-dioxaphosphorinane,
protective ‘fabric bag and placed in la tumbling water bath
Z-methyl-4-methoxymethyl-1,3,Z-dioxaphosphorinane, and
at a temperature of 50° C. for about 30 minutes to e?ect
solvation of the resin. Heating was continued for two
hours at a temperature of 80° C. whereby :a clear resin
solution was obtained containing 25 percent solids and
the like.
The triorgano-phosphoius compounds of this inven
tion are effective as stabilizers when incorporated in the
halogen-containing vinyl resin compositions in small
amounts effecting concentrations in the resin composi
tions of from about 0.01 percent to about 1.0 percent
phosphorus by weight of resin.
The concentration of
stabilizer to be employed is therefore a function of the
molecular weight of the particular triorgano-phos
phorus compound utilized.
suitable for the spinning of synthetic ?bers. The color
50 of the resin solution was then determined quantitatively
Especially good results
by measuring the transmission of light at a wave length
of 430 rnillimicrons through :a solution containing 4 per
cent resin and 12 percent acetone by weight, ‘and pre
pared by weighing out approximately 5 grams of the
resin solution into a two-ounce glass vial and adding
thereto \a volume of dimethyl tormamide which in cubic
centimeters Was equal to 5.3 times the weight of the resin
solution in grams.
about 0.3 percent phosphorus by weight of resin.
The results obtained tirom these experiments are tabu
Little increase in the resistance of the resin compositions 60 lated below in Table A. Included in the table vfor com
to discoloration by heat or light is realized by the use of
parison are results obtained from similar experiments,
stabilizer concentrations above this preferred range, while
in which, however, stabilizers other than those included
the stability of the resin compositions decreases propor
within the scope of this invention such as dioctyltin male
are obtained when the triorgano-phosphorus compounds
are present in the resin compositions in amounts ef
fecting concentrations of from about 0.05 percent to
tionally with decreasing stabilizer concentrations below
this range. Although the stabilizers can be employed in 65
amounts effecting concentrations of phosphorus in the
resin compositions in excess of about 1.0 percent by
weight of resin, attendant disadvantages, such as bad
odor or alteration of the physical properties of the resin,
generally prevents the satisfactory utilization of the sta
bilized resin compositions so obtained.
i
ii
The method of incorporating the triorgano-phosphorus
compounds in the resin compositions is not critical to
the invention. For example, when it is desired to pro
ate, tri-(2-chloroethyl) pho-sphite, d-ibutyl phosphite, di
(Z-ethylhexyl) phosphite, diphenyl phosphite, diisopropyl
phosphite, Z-ethylhexyl octylphenyl phosphilte and tri
phenyl phosphite, were employed. Also included in the
table are results obtained from control samples contain
ing unstabilized resin solutions. One such control was
prepared as described above but was not subjected to
heat treatment. In the table, “color values” represent the
percent transmission of light at a wave length of 430
millimicrons through the resin solution, with high “color
In certain instances Gardner
vide stabilized resin solutions such as those in common 75 values” being preferred.
3,055,861
7
8
.
values are also indicated, Higher Gardner values corre
spond to yellower or darker resin solutions. The “color
values” for the stabilized resin solutions were in all in
stances, measured after heat treatment.
chilled dimethyl formamide was employed as solvent in
another group. The resin used in this series of experi
ments was a terpolymer of vinyl. chloride (20 percent),
vinylidine chloride (11 percent) and acrylonitrile (69 per
cent), having a molecular weight such that the speci?c
viscosity of an 0.2 percent solution of the resin in dimethyl
Table A
formarnide at a temperature of 29° C. was 0.334. The
resin was added to the solvent at room temperature and
Stabilizer
Color
values
solvation carried out by heating at a temperature of 90° C.
Gardner
values
Controls:
10 for about 30 minutes, followed by an additional heating
period of about three hours at the same temperature. The
results obtained from the experiments, tabulated below in
None (unheated resin solution)
None (heated resin solution)
Table C, again indicate the improved resistance to dis
coloration that is obtained when utilizing the stabilizers
Triorgano-phospllorus compound
'l‘riethyl phosphite
Tri-(Zethylhexyhp spl
'l‘ri utyl phosp iito__ __
of this invention. The “color values” for the stabilized
resin solutions were in all instances measured after heat
Trihexyl phosphite ________ __
treatment.
Trigentyl phos hi
Triisooctylphosphite ____ _.
Table C
Trideeyl phosphite-.
Tridodecyl phosphite"
.
Tripropenyl phosphite ______________________ ._
'I‘ri-(Q-methylgropenyl) phosphite
Dipropenyl p enyl phosphite _______________ __
Diphenyl methyl phosphite _________________ ._
Color
Color
values in
values in
acetonitrile dimethyl
solution iormamide
solution
Stabilizer
Dibutylphenyl hosphite
Tri-(Z-phenoxyet iyl) phosphite _____________ __
‘Tributyl phospnine _________ .
Triphenyl phosphine ______ __
Dibutyl phenylphosphonite...
242-hydroxyethoxy)-1,3.2-di0xap .p
n ___
2-methoxy-4-propyl-?-ethyl-l, 3, 2-dioxaphos
phorinane.
2-phenoxy~4. 4, o-trimethyl-l, 3, Zdtoxaphos
phorinane.
Controls:
None (unheated resin solution) __________ __
None (heated resin solution) ____________ __
Triorgano-phosphorus compounds:
Tributyl phosphite ______________________ _.
Trihexyl phosphite _______________ -_
Other stabilizers:
_
Tri-(Zethylhexyl) phosphite ____________ __
Dioctyltin maleate __________________________ __
30
Tri-(2~chloroethyl) phosphite
Di-(‘z-ethylhexyl) phosphite.
Diphenyl phosphite
Dibutyl phosphite ________ __
Triisooctyl nh?snhifo
Other stabilizers:
Dioctyltin maleate ______________________ ._
Dibutyl phosphite ______________________ __
Diisopropyl phosphite _______ __
2ethyll1exyl octylphenyl phosp ite__
_
EXAMPLE III
Triphenyl phosphite ________________________ __
35
A series of experiments was conducted in a manner
similar to that described in Example I, modi?ed as indi
cated below. Unchilled acetonitrile was substituted for
From the above table the improved resistance to dis
acetone as the solvent. Tht resin used in this series of
coloration that is obtained when utilizing the stabilizers
of this invention is readily apparent. Those resin solu 40 experiments was a copolymer of vinyl chloride (33 per
cent) and acrylonitrile (67 percent) having a molecular
tions having lower resistance to discoloration possess
weight such that the speci?c viscosity of an 0.2 percent
higher Gardner values and lower “color values,” the
solution of the resin in dimethyl formamide at a tempera
latter signifying the transmission of less light through the
ture of 20° C. was 0.372. The results obtained from the
solutions as a result of increased color development dur
experiments, tabulated below in Table D, further indicate
the improved resistance to discoloration that is obtained
when utilizing the stabilizers of this invention. The “color
ing heat treatment.
Additional experiments were performed as described
above in which, however, in one group unchilled aceto
values” for the stabilized resin solutions were in all in
stances measured after heat treatment.
Table D
nitrile was substituted for acetone as the solvent, and in
another group, unchilled dimethyl formamide was em
ployed as solvent. The results obtained from these experi
ments are shown in Table B. The “color values” for the
stabilized resin solutions were in all instances measured
after heat treatment.
Table B
Stabilizer
Stabilizer:
Controls:
None (unheated resin solution) _______ __ 82.0
None (heated resin solution) _________ __ 70.5
55
Color
Color
values in
values in
Triorgano-phosphorus compounds:
Tributyl phosphite _________________ __ 74.5
Trihexyl phosphite _________________ __ 74.5
Tri-(2-ethylhexyl) phosphite _________ .. 77.0
acetonitrile dimethyl
solution iormamide
solution
Color values
Conventional stabilizers:
60
Dioctyltin maleate __________________ __ 73.0
Dibutyl phosphite __________________ __ 68.0
Controls:
_
None (unheated resin solution) __________ __
None (heated resin solution) ____________ .-
Triorgano~phosphorus compounds:
Tributyl phosphite . _ . _ . . _ _ _
87
67. 5
87
61. 5
EXAMPLE IV
A series of experiments were conducted in a manner
_ _ _ _ _ . . ._
84. 5
85.0
Triisooctyl phosphite ____________________ __
83. 5
83. 5
77
70
76. 5
67
Other stabilizers:
Dioctyltin maleate ______________________ -Dibutyl phosphite ______________________ __
65 similar to that described in Example I using the same resin
and solvent described therein, modi?ed as indicated below.
The stabilizers employed were triethyl phosphite, tributyl
phosphite, trihexyl phosphite, tri-(Z-ethylhexyl) phosphite
EXAMPLE II
A series of experiments was conducted in a manner
similar to that described in Example I, modi?ed as indi
cated below. Unchilled acetonitrile was substituted for
and triisooctyl phosphite. The experiments were carried
70 out utilizing each stabilizer in concentrations of 0.25, 0.5,
1.0, and 2.0 percent phosphite by weight of resin. The
results obtained from the heated resin solutions are
tabulated below in Table E. In the table, stabilizer con
centrations are indicated both as percent phosphite and
acetone as solvent in one group of experiments and un 75 as percent phosphorus by weight of resin in the solutions.
3,055,861
9
Table F
Table E
Concentra
TRIETHYL PHOSPHATE
_
Goncentration of phosphite (percent)
Concentra
Concentration of phosphitc (Percent)
tion of
phosphorus
tion of phos- Time (min)
phorus (per
cent)
Color
values
0.019
0. 037
0. 074
0.14
0.22
(Percent)
0. 047
0. 094
0.19
0.37
84
10 to 20
30 to 60
90 to 120
120
180
From the table it can be seen that where greater quanti
ties of stabilizer are used, good color characteristics for
the resin solution can be maintained for longer periods
of time; conversely, with lesser quantities, good color
66
characteristics can still be realized, but for shorter periods
of time.
EXAMPLE VI
74
83
84
A series of experiments was conducted in a manner
similar to that described in Example I, modi?ed as indi
66
74
cated below. Unchilled acetonitrile was substituted for
acetone as solvent. The resin employed was a copolytner
82
of vinylidine chloride (44 percent) and acrylonitrile (56
84
percent), having a molecular weight such that the spe
25 ci?c viscosity of an 0.2 percent solution of the resin in
dimethyl formamide at a temperature of 29° C. was
0.019
0.037
0. 074
0. 15
64
68
77
84
0.414. The results obtained from the experiments, shown
below in Table G, further indicate the improved resistance
to discoloration that is obtained when utilizing the sta
30 bilizers ‘of this invention. The “color values” for the
stabilized resin solutions were in all instances measured
PHOSPHITE
after heat treatment.
0.019
0.037
0. 074
64
68
79
.15
84
Table G
Stabilizer:
Color values
Control:
None (unheated resin solution) ______ __' 81.0
None (heated resin solution) _______ __ 70.20
Triorganoephosphorus compounds:
From the table it may be seen that the stabilizers of this
invention are essentially equivalent in their ability to 40
improve resistance to discoloration when present in
amounts effecting equal concentrations of phosphorus in
the resin solutions, the concentration of phosphorus pres~
ent being a function of the molecular weight of the partic
ular stabilizer employed.
Tributyl phosphite __________________ __ 86.0
Trihexyl phosphite _________________ __ 83.0
Tri—(2»ethylhexyl) phosphite ________ __ 81.0
Other stabilizers:
Tri-(2-chloroethyl) phosphite ________ __ 76.5
Dibutyl phosphite __________________ __ 77.5
45
It can also be observed from the table that the use
of the stabilizers in amounts effecting concentrations
EXAMPLE VII
A series of experiments was conducted in a manner
of greater than about 10.1 percent phosphorus by weight
similar to that described in Example I, modi?ed as in
dicated below. Unchilled acetonitrile was substituted for
of resin in the solution does not substantially further
improve the color characteristics of the resin solution, 50 acetone as solvent in one group of experiments, and un
chilled dimethyl tormarnide used as solvent in another
the “color values” of the solutions being essentially con
group. The resin employed in this series of experiments
stant ‘at higher ‘concentrations. It is to be noted in this
was a copolymer of vinylidine chloride (46 percent)
respect, however, that the use of higher stabilizer con
and acrylonitrile (54 percent) having a molecular weight
such that the speci?c viscosity of an 0.2 percent solution
centrations generally will permit maintaining the resin
solutions at a desirable color level for prolonged periods
of time. This may be seen from the following example.
of the resin cyclohexanone at a temperature of 20° C.
was 0.254. The results obtained from the experiments,
tabulated below in Table H, again illustrate the improved
EXAMPLE V
similar to that described in Example I, using the same
resistance to discoloration that is obtained when using the
The “color values” for the
stabilized resin solutions were in all instances measured
resin and solvent described therein. In this series of ex
after ‘heat treatment.
A series of experiments was conducted in a manner 60 stabilizers of this invention.
periments tri-(2-ethylhexyl) phosphite was incorporated
Table H
in the solutions in concentrations of 0.25, 0.5, 1.0, 2.0 and
3.0 percent phosphite by weight of resin, corresponding
65
Color
values in
to concentrations of phosphorus in the resin solutions
Stabilizer
of 0.019, 0.037, 0.074, 0.14 and 0.22 percent by Weight
of resin respectively. ‘For each run, the length of time
during which the stabilized resin solution could be main
tained at a temperature of 80° C. without having the 70
“color value” drop below 84 was determined. The re
sults obtained are tabulated below in Table F. In the
table, the concentrations are indicated both as percent
phosphite and as percent phosphorus by weight of resin
in solution; the time is indicated in minutes.
75
Color
values in
acetonitrilo dimethyl
solution formamide
solution
Controls:
None (unheated resin solution) ____ __
83.5
83. 5
76. 5
60.0
_
___
86.5
84. 5
74. 5
72.0
Other stabilizers: Dibutyl phosphite ________ __
79. 0
65.5
None (heated resin solution)
Triorgano-phosphorus compoun
Tributyl phosphito _______ __
Triisooctyl phosphite ________ __
3,055,861
11
12
EXAMPLE VIII
a stabilizer therein a triorgano phosphine represented by
the formula
A series of resin solutions was prepared in a manner
similar to that described in Example I using the same
R
/
resin and solvent, and described therein each containing
one of the following stabilizers: 1 percent tributyl phos
P-Rl
\R2
phite, .1 percent trihexy-l phosphite, 1 percent triisooctyl
phosphite and 2 percent triisooctyl phosphite. One resin
wherein R, R1 and R2 represent hydrocarbyl radicals
containing up to 12 carbon atoms, said triorgano phos
phine being incorporated in said resin solution in an
solution was also prepared containing no stabilizer.
From these resin solutions staple ?bers were obtained
by identical extrusion and coagulation procedures in 10 amount effecting a concentration therein of from about
0.01 percent to about 1 percent by weight of phosphorus
accordance with conventional spinning techniques. The
based upon the weight of resin.
?bers were tested for light stability by measuring the
2. The stabilized resin solution as claimed in claim 1
percent re?ectance of monochromatic light at a wave
wherein the triorgano phosphine is tributyl phosphine.
length of 440 millimicrons. Readings were taken initially
3. The stabilized resin solution as claimed in claim 1
and at twenty-hour intervals for a total period of 80 15
wherein the triorgano phosphine is triphenyl phosphine.
hours’ exposure in an Atlas Fade-Ometer. The results
obtained are set forth below in Table I, wherein “re
4. A stabilized resin solution comprising an inert or
ganic solvent solution of a resin copolymer of acrylonitrile
?ectance values” represent the percent light re?ectance
with at least one member selected from the group con
of each ?ber after exposure in the Atlas Fade-Ometer
for the indicated periods of time, with high “re?ectance 20 sisting of vinyl chloride and vinylidene chloride, said co
polymer containing in polymerized form from about 15
values” being preferred. Also tabulated for each ?ber
percent to about 70 percent by weight of the chlorine
is the percent drop in light re?ectance after 80 hours’
containing monomer, said resin solution incorporating
exposure, calculated as follows:
a stabilizer therein a triorgano phosphinite represented
Re?ectance value (0 hours) —re?ectance value (80 hours) 25 as
by the formula
Re?ectance value (0 hours)
R
X 100=percent drop in re?ectance (after 80 hours)
/
P-Rl
Table I
Re?ectance values
Per
cent
Stabilizer
0 hrs.
20
40
60
80
hrs,
hrs.
hrs.
hrs.
None ....................... ._
63
50
41
35
31
1 percent tributyl phosphite__
1 percent trihexyl phosphite__
1 percent triisooctyl phosphite.
2 percent triisooctyl phosphite.
72
74
78
79
64
66
71
76
58
63
65
71
54
58
61
67
49
63
56
66
ORz
30
drop in
re?ec
tance
wherein R, R1 and R2 represent hydrocarbyl radicals con
taining up to 12 carbon atoms and wherein the radical
represented by R2 is attached to the vicinal oxygen atom
of said triorgano phosphinite by an aliphatic carbon atom,
35 said triorgano phosphinite being incorporated in said resin
solution in an amount effecting a concentration therein of
31. 9
50. 0
28. 4
28. 2
16. 4
The e?ectiveness of the stabilizers of this invention can 40
be seen from the above table as represented by the drop
in re?ectance values over the 80-hour period, Which is
a measure of the increased darkening or yellowing of the
?bers. The ?bers containing the stabilizers show consid
erably less discoloration with time, i.e. lower percent drop
in re?ectance values, when exposed to light as compared
from about 0.011 percent to about 1 percent by weight of
phosphorus based upon the weight of resin.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,456,216
Richter _____________ __ Dec. 14, 1948
2,564,646
Leistner et al. ________ __ Aug. 14, 1951
2,824,845
Kosmin _____________ __ Feb. 25, 1958
2,834,798
Hechenbleikner et al. ____ May 13, 1958
2,867,594
2,878,227
2,878,229
2,885,377
2,894,923
Hanson et al. _________ __ Ian, 6,
Ucci et al ____________ __ Mar. 17,
Jenkins et al __________ __ Mar. 17,
Knowles et al. ________ __ May 5,
Graham _____________ __ July 14,
ing of vinyl chloride and vinylidene chloride, said co
polymer containing in polymerized form from about 15
percent to about 70 percent by weight of the chlorine
2,946,764
Toy et al. ___________ __ July 26, 1960
containing monomer, said resin solution incorporating as
1,119,752
France ________________ __ Apr. 9, 1956
with ?bers containing no stabilizer.
What is claimed is:
l. A stabilized resin solution comprising an inert or
ganic solvent solution of a resin copolymer of acrylonitrile 50
with at least one member selected from the group consist
1959
1959
1959
1959
1959
FOREIGN PATENTS
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