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Патент USA US2115708

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I Patented-May 3, 1938
‘ NlTE
Henry Dreyfus, London, England
No Drawing. Application February 8, 1934, Se
rial No. 710,346.. In Great Britain February it,
11 Claims“ v ((21. 106—-4i®)
This invention relates to the manufacture of
products made of or containing derivatives of
cellulose, synthetic resins and other plasticizable
substances, and particularly to the manufacture
The presence of halogens in such compounds in
general tends to increase their resistance to ?re,
a property which is of considerable value in com
positions containing in?ammable substances such
5 and application of a new class of plasticizer.
The plasticizers of the present invention are
unsymmetrical and other esters of polycarboxylic
acids containing at least one substituted or un
substituted residue of a dihydric alcohol or de
reaction between substituted or unsubstituted
glycols (or di- or 'polyglycols) or mono-ethers
lo rivative thereof, excluding the symmetrical esters
of such acids with unsubstituted glycols. The
term "polycarboxylic acid” is used here to de
thereof and polycarboxylic acids or their anhy
drides in presence or absence of catalysts such
for example as sulphuric acid, or between ole?ne
note acids containing more than one carboxyl
group and the term “residue bf a dihydric alco
15 hol” to denote the residue obtained by removing
one hydroxy group from a dihydric alcohol in
hydrins or derivatives thereof and salts,-for ex
ample the sodium or silver salts or polycarboxylic
as nitrocellulose.
Some general methods for producing the esters
of the invention are the following: by effecting
oxides and polycarboxylic acids; between halo
which one or more of the hydrogen atoms may
acids or their acid esters; between mono-halo
gen-alkyl ethers and salts of mono-esters of
or may not be substituted for example by alkyl
poly'carboxylic acids; or between salts of acid
esters of polycarboxylic acids, containing ‘free or
The esters of the invention are new chemical - etheri?ed'dihydric alcohol residues, and esters ‘_
of halogenated fatty acids, or by the hydrolysis
substances and the invention includes their pro
of phthalic acid esters containing esteri?ed '
duction and the esters themselves.
dihydric alcohol residues, or of mixed esters con
The acids of which the new esters are deriva
groups or halogen atoms. '
tives may be cyclic compounds, for example
25 phthalic acid and its halogen or alkyl substitu
tion products. or acyclic compounds,- e. g. ma
lonic, glutaric, succinic and. tartaric acids and
their substitution products.
taining a dihydric alcohol residue and a more
easily removed esterifying group.
. The following are someltypical phthalic acid ,
esters of the new class and. methods for their
production; mono-(p-hydroxyethyl) phthalate,
The esters may contain in addition to the free
v30 or etheri?ed dihydric alcohol residue a hydro
carbon residue, especially a methyl group, or a
produced from phthalic anhydride and ‘glycol;
mono-(p-ethoxyethyl) phthalate, produced’ from
phthalic anhydride and p-hydroxyethyl ether;
diiferent dihydric alcohol residue in which the
methyl-(?-hi'droxy-ethyl) phthalate, from sodi
um methyl phthalate and ethylene chlorhydrin,
hydroxy group may or may not be etheri?ed or
esteri?ed. Thus among esters containing a hy
drocarbon group in addition to the dihydric al
‘or from mono-(?-hydroxyethyl) 'phthalateland
cohol residue are the alkyl hydroxy-alkyl series,
especially the methyl-hydroxy-alkyl series and
phthalate, from sodium methyl phthalate and
methyl - (p -, ethoxy - ethyl)
mono-chlor-ethyl ether or from mono-(?-ethoxy- ‘
compounds in which the alkyl group contains a ‘ ethyl)‘ phthalateand methyl alcohol; p-acetoxy
ethyl-(?—methoxy-ethyl) phthalate, produced by
considerable number, for example 6 or more car
40 bon atoms, and the alkyl alkoxy-alkyl series.
Among those containing two dihydric alcohol
residues are those containing two similarly con
- stituted derivatives of different dihydric alcohols,
e. g. two di?erent hydroxy-alkyl or alkoxy-alkyl
45 groups, and those containing two differently con
,stltuted'groups which may or may not be de
rivatives of the same dihydric alcohol, e. g. hy
droxy-alkyl alkoxy-alkyl, acidyl-hydroxy-alkyl
alkoxy-alkyl and hydroxy-alkyl ‘acidyl-hydroxy
50 alkyl, hydroxy-alkyl alkyl-carboxy-alkyl and
alkoxy-alkyl alkyl-carboxy-alkyl esters.
?-hydroxy-ethyl-(p - methoxy
ethyl) phthalate; B-acetoxy-ethyl-(p-ethoxy—
ethyl) phthalate, produced by acetylating p-hy
droxy - ethyl — (p - ethoxy - ethyl)
phthalate; _
acetoxy-ethyl-(B-hydroxy-ethyl) phthalate, pro—
duced by partial hydrolysis of di-(p-acetoxy
ethyl) phthalate; and ?-methoxy-ethyl-(ethyl
carboxy-methyl) phthalatefproduced from the
sodium salt of mono-(p-methoxy-ethyl) phthal
ate and ethyl chlor acetate.
Those esters are to be preferred which do not 50
give an acid reaction even after long storage or
The esters may contain substituted cyclic, for ‘ use. Should it however appear desirable for
example benzoid, groups as well as substituted some special purposes'to make use of esters
. alkyl groups. Thus for example the esters may which are acid or may develop acidity, anti-acid
55 be derivatives of halogenated phthalic acids. ‘ bodies, for example tetra-methyl urea and simi- I
lar alkylated amino bodies may with advantage
be included in compositions containing the esters.
The invention includes the application of the
new plasticizers generally in the manufacture of
articles or materials comprising cellulose acetate,
nitrocellulose, synthetic resins and like plasticiz
able substances, for example by moulding, ex
trusion, evaporation of solvent, coagulation by
liquid media, spreading or spraying methods, and
10 includes products, materials and compositions of
matter which contain the plasticizers or in the
manufacture of which the plasticizers are used,
for example moulding powders, moulded or ex
truded articles, sheets, ?lms, ribbons, ?laments,
15 arti?cial
paper, arti?cial leather, splinterless
glass, lacquers, varnishes, enamels and coating
compositions generally, whether for application
to ?brous or non-?brous materials.
The new esters are of particular value when
20 the plasticizable material comprises an organic
ester of cellulose, for example an ester such as
cellulose i‘ormate, propionate, butyrate and par
, 'ticularly cellulose acetate, or an ether such as
methyl, ethyl or benzyl cellulose.
esters or ethers may be esteri?ed or etheri?ed to
any desired degree, for instance I may employ
cellulose acetates having an acetyl content lying
between that of the triacetate and the diacetate,
such as the esters obtainable by hydrolyzing or
30 “ripening” a triacetate to an acetyl content in
the neighbourhood of 58% combined acetic acid,
or till it becomes soluble in acetone. The cellu
lose derivative may have any desired viscosity
characteristics according to the purpose ‘for
which it is to be employed. In the production of
lacquers and other coating compositions cellulose
derivatives of relatively low viscosity may gen
erally be used. Where, however, tensile strength
is a desideratum in the product, it is preferable
40 to employ esters of high viscosity.
The produc
xylenes, cumene, cymene or other hydrocarbons
of low, medium or high boiling point. For ex
ample, coating compositions may contain in addi
tion to plasticizable material and one or more of
the new plasticizers, a low boiling solvent for the
material, a medium boiling non-solvent therefor
with. or without additional high boiling solvents
or plasticizers, for example, glycerin, triacetin,
tributyl phosphate, triphenyl phosphate, tricresyl
phosphate, dibutyl tartrate, triphenylol propane
or a plasticizer of the sulphonamide or sulphon
anilide series. Non-in?ammators may also be
present and these may themselves function as
plasticizers, as to, for example, tri-brom acetani
lide and other halogenated acidylated aromatic
Solvents, latent solvents, diluents and non
solvents for the plasticizable material may be
employed in the manofacture even of solid prod
ucts. For example in the manufacture of ?la
ments, ribbons and the like by evaporative proc
esses, the dope will in general contain, in addi
tion to the plasticizable material and a relatively
small proportion of plasticizer, a relatively large
proportion of a volatile solvent or solvent mix 25
ture. The solvent mixture may comprise two or
more latent solvents which together form a sol
vent mixture, and/or may contain suitable non
solvents, provided these are not present in su?i
cient quantity to cause precipitation of the plasti 80
cizable material at too early a stage in the evapo
ration. Dopes for the production of ?laments,
ribbons, ?lms and the like by the wet process may
also contain such liquids, though in this case it
is not of course necessary that the major part 85
of the solvent or solvent mixture should be vola
tile, the essential being that a su?lcient propertion of the solvent should be removable by the
coagulating medium.
The plasticizers may be introduced into the 40
tion of such esters is described in U. S. Patent
product, material or composition at any conven
No. 1,708,787.
The products and ~compcsitions of the inven
ientrstage in the manufacture thereof and by
tion may contain natural or synthetic resins, for
ucts formed from liquid compositions‘ or dopes,
for example by extrusion, evaporation, coagula 45
tion by liquid media or by spreading, it may be
convenient to introduce the plasticizers into the
example shellac, dammar, phenol aldehyde resins
of the soluble fusible type whether in the Novolak
or Resol stage, and soluble fusible resins from
other starting materials, for instance from di
phenylol propane and formaldehyde or from
50 other aldehydes, from urea or thiourea and form
aldehyde, and particularly synthetic resins of the
polymerized vinyl ester type, for example poly
merized vinyl acetate.
Many of the compositions will naturally con
55 tain in addition to the new plasticizers and the
plasticizable material volatile solvents or solvent
mixtures therefor. For example, liquid compo
sitions containing cellulose acetate may contain
acetone, methyl ethyl ketone, ethyl formate, di
oxane, and other volatile solvents. High boiling
solvents, for example cyclohexanone, ethyl lac
tate, diacetone alcohol, benzyl alcohol and cyclo
hexanol may also be present. The compositions
may contain latent solvents for the cellulose de
65 rivative, for example ethyl alcohol, methyl alco
hol and, other aliphatic alcohols of low molecular
weight, ethylene and methylene chloride and
other halogenated aliphatic hydrocarbons. There
may be present two or more latent solvents which
70 together form a solvent mixture for the cellulose
any convenient means. In the case of solid prod
dope directly or in solution or suspension in a
suitable liquid. In the manufacture of moulding
powders and the products made therefrom, the 50
plasticizer may conveniently be introduced in the
process of malaxation or may be sprayed on to
the cellulose derivative in the form of a solu
tion in a volatile solvent, as described in U. S.
applications S. Nos. 525,617 and 525,618, ?led 55
26th March, 1931.
Other constituents of the products, materials
or compositions may include oils, waxes, ?lling
agents, white or coloured pigments, organic col
ouring agents, and/or substances adapted to pro 60
duce particular effects, e. g. pearl essence and
powdered metals. The materials may be sub
jected to after treatments with a view to chang
ing their physical or even chemical character
istics, according to the properties required.
The following examples illustrate the inven
tion without in any way limiting it:
Ercample 1
acetate, for example mixtures of ethyl or ‘methyl
alcohols with ethylene 'or methylene dichlorides.
100 lbs. phthalic anhydride are heated with 50
lbs. monomethyl glycol ether and a small quan
The compositions may moreover contain diluents
or non-solvents for the cellulose derivative, for
75 example benzene, toluene or any of the three
tity of sulphuric’acid to act as a catalyst, to a
temperature of 140° C. under a fractionating
column by means of which the water produced
in the reaction is slowlyremoved while the less
volatile monomethyl glycol ether is returned to
the reaction. The product of the reaction, mono
Example 6
The potassium salt of mono-u-ethyl-butyl
phthalate in a ?nely divided form is heated with
p-chlordiethyl ether under re?ux for 10 hours.
(e-inethoxy-ethyl) phthalategon violent shaking
d or “seeding” crystallizes out.
A. similar reaction may be employed for the
The a-ethyl-butyl-(?-ethoxy-ethyl)
ethyl acetate, ?ltered from the potassium chlo
ride formed, and recrystallized from‘ the solvent
phthalate, in which the starting- materials are
phathalic anhydride and ‘the monomethyl ether
W of diethylene glycol.
its weight of dilute sulphuric acid for from 27-3
hours, with the production by hydrolysis of 15
_ tairied in Example 1 may be converted into B
p-methoxy-ethyl p-hydroxy-ethyl phthalate.
10b lbs'. of mono-(B-methoxy-ethyl) phthalate
Example 8
A cellulose acetate plastic composition contain
ing as plasticizer p-hydroxy-ethyl-(e-methoxy 20
ethyl) phthalate may be made up as follows:-—
30 parts of the B-hydroxy-ethyl-(p-methoxy
is heated in an autoclave with 60 lbs. of ethylene
oxide at a temperature of 100° C. for about 9
0 hours. At the end of this time a further so lbs.
' of ethylene oxide is added, and the reaction con
tinued under the same conditions for a further
period of 9 hours. The product is neutralized
25 with suiiicient sodium carbonate to combine with
the unchanged mono-(B-methoxy-ethyl) phthal
ate remaining and is then-washed several times
ethyl) phthalate are dissolved in 120 parts or a
50:50 alcohol benzene mixture and the solution is
thoroughly incorporated with 100 parts of acetone 25
soluble cellulose acetate.
way. ‘The plasticized mass thus produced may.
be employed for the manufacture of moulded 30
products of any desired form.
Example 3
phthalate; in the
form of its sodium salt, may also be converted
into B-m'ethoxy-ethyl-(?-acetoxy-ethyl) phthal
35‘ ate'in the following way:
601 lbs. of mono-(B-methoxy-ethyl) sodium
phthalate is powdered and heated with 120 lbs.
,B-chlorethyl acetate under reflux until a sub
stantially complete esteri?cation is obtained.
40 The reactants are then allowed to cool to about
45° (3., and ?ltered to remove the sodium chloride
formed in the reaction. The chlorethyl acetate
is then removed by distillation. If desired a ?nal
puri?cation of the p-methoxy-ethyl-(p-acetoxy
Example 9
A composition which may be employed for the
formation of lacquers or insulating coatings is:— as
Cellulose acetate_____________________ __‘___
Polymerized vinyl acetate _________ __' ____ __
phthalate ________________________ __-____
Example 10
Another composition that is suitable‘ for the
Example 4
formation of lacquers is:-
.p-methoxy-ethyl-(B-acetoxy-ethyl) phthalate
~10 may also be prepared by acetylation' of p-meth~
following description indicates one method where
by this may be accomplished.
Equal molecular proportions of B-methoxy
ethyl-(p-hydroxy-ethyl) phthalate and acetyl
cooled so as to maintain a temperature of from
25°-30° C. When substantial evolution of hydro
chloride ceases the mixture is heated to 40°
C. for about an hour and any excess acetyl chlo
ride is destroyed by adding water. Acetic acid
‘Nitrocellulose __________________________ __
15 50
B-ethoxy-Jethyl- ( p-acetoxy- ethyl)
Triphenyl phosphate _____ _l ____ __- ______ __
Butyl acetate ____________________ __' ____ __ 1000
The following composition is very suitable for
producing highly ?exible ?lms or coatings which
may be used for covering rubber insulated cables
or the like:—
Cellulose acetate________________________ __ 100
Diphenylol propane formaldehyde resin____ 20
Example 5
tartrate ____ __' __________________ __ 200,
Monomethyl sodium phthalate is heated with
a molecular equivalent of ethylene chlorhydrin in
Mono-a-ethyl-butyl- ( ?—ethoxy-ethyl)
an autoclave to a temperature of 140° C. for some
Acetone ________________________________ __ 400
Dloxane ___________________________ __'____..- 250
The reactants are then allowed to cool,
and the methyl-(p-hydroxy-ethyl)
iormed is dissolved in a mixture of alcohol and
ethyl acetate, separated from insoluble impuri
ties by ?ltration, and ?nally purified by fraction
75 al distillation under reduced pressure.
Example 11
so formed is removed with the water by distilla
tion, preferably under reduced pressure.
Diphenylol propane formaldehyde resin...
chloride are carefully mixed and the mixture
Benzene ____ ..._...__l _____________________ .._ 25d
. under very low pressure.
______ __
Alcohol ________________________________ __ 250
45_ethy1) phthalate may be eifected by distillation
oxy - ethyl - (p - hydroxy - ethyl)
The incorporation is
effected byvmeans of malaxating rollers, the sol-'
vent being removed by evaporation in the usual
The product is .
' then dried at a temperature of 90° Ciiunder re
duced pressure.
p-methoxy-ethyl-(p-acetoxy-ethyl) phthalate
15’ hydroxy-ethyl-(p-methoxy-ethyl) phthalate in
is gently heated under re?ux with from 3-5 times
."li‘he mono-(p-methoxy-ethyl) phthalate ob
with small quantities of water.
Example 7
Example 2
“’ vtheufollowing way:--
formed is dissolved in a mixture of benzene and
production of mono-(methoxy-p-ethoxy-ethyl)
phthalate ______ -7 ___________ -l _______ __
What I claim and desire to secure by Letters
Patent is:—
1. Compositions and articles containing a de
rivative of cellulose, selected from the group con
sisting of organic acid esters of cellulose, methyl
cellulose, ethyl cellulose and benzyl cellulose, and
an ester of a polycarboxylic acid, said ester con
a basis of a derivative of cellulose, selected from
the group consisting of organic acid esters of
taining groups of the formulae --COQ.R1OH and
-—COO.R2OR3, where R1, R2 and R3 are saturated
benzyl cellulose, and an ester of a polycarboxylic
aliphatic hydrocarbon radicles.
2. Compositions and articles containing an
organic acid ester of cellulose and an ester of a
polycarboxylic acid, said ester containing groups
of the formulae —COO.R1OH and —~COO.R2OR:,
10 where R1, R2 and R3 are saturated aliphatic hy
drocarbon radicles.
3. Compositions and articles containing cellu
lose acetate and an ester of a polycarboxylic acid,
said ester containing groups of the formulae
—"COO.R'1OH and -COO.R2OR3, where R1, R2
and R3 are saturated aliphatic hydrocarbon radi
4. Compositions and articles containing an or
ganic acid ester of cellulose and an ester of the
20 formula
where R1, R2 and R3 are saturated aliphatic hy
drocarbon radicles.
5. Compositions and articles containing an or
ganic acid ester of cellulose and an ester of a
halogenated phthalic acid, said ester contain
ing groups of the formulae --COO.R1OH and
—COO.R2OR3, where R1, R2 and R3 are saturated
aliphatic hydrocarbon radicles.
6. Compositions and articles containing cellu
lose acetate and ?-hydroxyethyl ,B-methoxyethyl
cellulose, methyl cellulose, ethyl cellulose and
acid, said ester containing groups of the formulae
—COO.R1OH and —-COO.R2OR3, Where R1, R2
and R3 are saturated aliphatic hydrocarbon rad
8. Arti?cial ?laments and other articles hav
inga basis of an organic acid ester of cellulose 10
and containing an ester of a polycarboxylic acid,
said ester containing groups of the formulae
—COO.R1OH and -COO.R2OR3, where R1, R2
and R3 are saturated aliphatic hydrocarbon radi
9. Arti?cial ?laments and other articles having
a basis of an organic acid ester of cellulose and
containing an ester of the formula
where R1, R2 and R3 are saturated aliphatic hy
drocarbon radicles.
‘10. Arti?cial ?laments and other articles hav
ing a basis of an organic acid ester of cellulose
and containing an ester of halogenated phthalic
acid, said ester containing groups of the formulae
-—COO.R1OH and —COO.R2OR3, where R1, R2 30
and R3 are saturated aliphatic hydrocarbon radi
11. Arti?cial ?laments and other articles hav
ing a basis of cellulose acetate and containing #
hydroxyethyl p-methoxyethyl phthalate.
7. Arti?cial ?laments and other articles having
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