U.S. patent number 3,839,207 [Application Number 05/374,190] was granted by the patent office on 1974-10-01 for allyl 2-carbamoyalkylphosphonates flame retardants.
This patent grant is currently assigned to Stauffer Chemical Company. Invention is credited to Edward D. Weil.
United States Patent |
3,839,207 |
Weil |
October 1, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
ALLYL 2-CARBAMOYALKYLPHOSPHONATES FLAME RETARDANTS
Abstract
The present invention provides a process for flame retarding
textiles, paper and other flammable, solid substrates by applying
to the substrate at least one allyl 2-carbamoylalkylphosphonate
corresponding to the formulae: ##SPC1## Where R is a hydrogen or
methyl radical, whereupon the phosphonate is cured by free radical
initiation so as to form an insoluble, fire retardant resinous
finish.
Inventors: |
Weil; Edward D.
(Hastings-on-Hudson, NY) |
Assignee: |
Stauffer Chemical Company (New
York, NY)
|
Family
ID: |
26836996 |
Appl.
No.: |
05/374,190 |
Filed: |
June 27, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
139222 |
Apr 30, 1971 |
3762865 |
|
|
|
Current U.S.
Class: |
526/278;
106/18.14; 525/54.23; 525/377; 8/194; 428/921; 525/326.6; 525/345;
526/261; 264/494; 987/353 |
Current CPC
Class: |
D21H
17/05 (20130101); D06M 13/288 (20130101); C08K
5/5373 (20130101); D21H 17/10 (20130101); C09D
5/18 (20130101); D06M 14/00 (20130101); C08J
7/16 (20130101); C07F 9/6521 (20130101); D21H
5/0002 (20130101); C07F 9/65742 (20130101); C07F
9/65746 (20130101); D21H 21/34 (20130101); Y10S
428/921 (20130101) |
Current International
Class: |
C09D
5/18 (20060101); B27K 3/34 (20060101); B27K
3/36 (20060101); C07F 9/00 (20060101); C08J
7/00 (20060101); C08J 7/16 (20060101); C07F
9/6521 (20060101); C07F 9/6574 (20060101); C08K
5/00 (20060101); D06M 13/00 (20060101); C08K
5/5373 (20060101); D06M 13/288 (20060101); D06M
14/00 (20060101); B27k 003/00 () |
Field of
Search: |
;8/116P ;252/8.1
;106/15FP ;117/136 ;260/66.5P |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Parent Case Text
This is a division of application Ser. No. 139,222 filed Apr. 30,
1971, now U.S. Pat. No. 3,762,865.
Claims
1. A flame retardant polymer of an allyl
2-carbamoylalkylphosphonate corresponding to the formulae:
##SPC5##
where R is selected from the group consisting of hydrogen and
methyl
2. The polymer of claim 20, wherein said allyl
2-carbamoylalkylphosphonate is selected from the group consisting
of diallyl 2-carbamoylethylphosphonate, diallyl
2-carbamoylisopropylphosphonate, N,N'-methylenebis(diallyl
2-carbamoylethylphosponate) and
3. The polymer of claim 1 wherein at least one other comonomer is
present in the polymer, said comonomer being selected from the
group consisting of amide nitrogen-containing monomers, monomers
containing more than one polymerizable double bond, and monomers
which contribute to flame retardancy and which have phosphorus,
bromine or chlorine atoms in their
4. The allyl 2-carbamoylalkylphosphonates corresponding to the
formula: ##SPC6##
where R is selected from the group consisting of hydrogen and
methyl
5. The compound ##SPC7##
6. The compound ##SPC8##
according to claim 4.
Description
BACKGROUND OF THE INVENTION
As shown, for example, in U.S. Pat. No. 3,374,292, it is known in
the textile and paper finishing art that cellulosic fabrics can be
flame retarded by applying compounds such as N-methylol
2-carbamoylethylphosphonates which are then cured on the substrate
by means of acid catalysts. However, there are several limitations
in this type of process including the fact that the resulting
finish is ineffective for flame retarding non-cellulosic fabrics
and is also unsatisfactory for blends of cellulosic and synthetic
fibers which contain a major proportion of non-cellulosic fibers.
In addition, such finishes require the use of acid catalysts at
elevated temperatures in the range of about 150.degree.-160.degree.
F. which leads to some acid catalyzed or thermal degradation of
cellulosic fabrics with a resultant loss of their physical
properties such as their tear strength. Moreover, because of the
elevated temperatures required for their application, sublimation
of these phosphonates, or of their decomposition products, can
occur causing sticky deposits as well as drippage in the curing
oven which often leads to spotting of the cloth and which may
require shutting down in order to permit cleaning of the equipment.
And, finally, the evolution of formaldehyde vapors from these
phosphonates creates an unpleasant atmospheric pollutant.
As is described in the U.S. Pat. Nos. 2,848,507 and 2,867,548, it
has also been known in the textile finishing art to use certain
diallyl phosphorus compounds such, for example, as diallyl
2-cyanoethyl phosphonate, in preparing flame retarding textile
finishes. However, the successful use of such compounds requires
their pre-polymerization which complicates the process and
necessitates the use of specific organic solvents with a resultant
high cost which is uneconomical for large scale commercial textile
finishing. Furthermore, these systems require high add-ons, i.e.
the deposition of high concentrations of reagents, with a resultant
poor "hand," i.e. unfavorable tactile qualities, stiffness and
harsh surface characteristics, in the resulting treated fabrics.
Because of these problems, these diallyl phosphonate finishes have
only had limited experimental use, particularly with heavy weight
military fabrics.
Thus, it is the prime object of this invention to provide a novel
flame retardant finishing process which is suitable for use with
textiles made from either natural or synthetic fibers as well as
with blends of each of the latter fiber types. It is another object
of this invention to provide a flame retardant finishing process
for various other flammable, solid substrates such, for example as
paper, wood, batting and rope, which are capable of being
impregnated and/or coated with a flame retardant, resinous finish.
It is a further object to provide a flame retardant textile
finishing process which is operable at ambient or moderately
elevated temperatures and which can employ aqueous systems thereby
avoiding fabric degradation and the need for expensive and
troublesome organic solvents. Another object is to provide a
process for flame retarding textiles which is operable with low
add-ons of the flame retardant finish thereby providing a pleasing
hand to the finished fabrics .
TECHNICAL DISCLOSURE OF THE INVENTION
This process comprises the application to a textile, or other
flammable solid substrate, followed by curing, of an effective
amount of at least one flame retarding allyl
2-carbamoylalkylphosphonate corresponding to the formulae:
##SPC2##
where R is a hydrogen or methyl radical. Exemplary of those
compounds are diallyl 2-carbamoylethylphosphonate, diallyl
2-carbamoylisopropylphosphonate, N,N'-methylenebis(diallyl
2-carbamoylethylphosphonate) and N,N'-methylenebis(diallyl
2-carbamoylisopropylphosphonate). These flame retardants are
applied to a fabric or other substrate at a concentration of from
about 5 to 40 percent, as calculated on the dry weight of the
substrate, and are thereafter cured, i.e. polymerized, so as to
form an insoluble, fire retardant resinous finish by free radical
initiation using either a chemical initiator or actinic radiation
in order to induce the desired reaction.
The diallyl compounds used as flame retardants in the process of
this invention, i.e. diallyl 2-carbamoylethylphosphonate and
diallyl 2-carbamoylisopropylphosphonate, are known and may be
readily prepared by the addition of diallyl phosphonate to either
acrylamide or methacrylamide as described, for example, in U.S.
Pat. No. 2,754,320, or by the addition of diallyl phosphonate to an
alkyl ester of acrylic or methacrylic followed by ammonolysis.
These diallyl compounds are crystalline, colorless solids of
negligible odor which are soluble in many organic solvents as well
as in water.
On the other hand, the above listed tetraallyl compounds, i.e.
N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate) and
N,N'-methylenebis(diallyl 2-carbamoylisopropylphosphonate), are new
compositions of matter which are prepared by means of the base
catalyzed addition of at least two moles of diallyl phosphonate per
mole of either N,N'-methylenebisacrylamide or
N,N'-methylenebismethacrylamide. In conducting this reaction, the
diallyl phosphonate and the N,N'-methylenebisacrylamide or
N,N'-methylenebismethacrylamide may be combined in the absence of a
solvent or, if desired, they may be slurried in a suitable
non-interfering solvent such, for example, as methylene chloride,
chloroform, carbon tetrachloride, benzene, toluene, acetone or
dioxane. The selected base catalyst, which can be sodium methylate,
an alkali metal hydroxide or any other suitable basic material, is
then introduced into the reaction mixture in a concentration of
from about 0.001 to 10 percent, as based upon the diallyl
phosphonate, resulting in an exothermic reaction which may cause
the mixture to boil. Trace solids are removed from the resulting
reaction mixture by filtration yielding the tetraallyl compound in
the form of a viscous syrup having a substantial degree of
solubility in water and organic solvents.
In addition to their use in the flame retardant finishing
application described herein, both the tetraallyl and the diallyl
2-carbamoylalkylphosphonates can be employed as monomers in the
preparation of flame retardant, thermoset homo- and copolymers
which can be used in a variety of applications including, for
example, as flame retardant additives for flammable polymers and
also as intermediates for preparing the flame retardant additives
and monomers such as those which can be made by the addition of
bromine to all or part of the double bonds of these compounds. For
purposes of brevity, the novel tetraallyl
2-carbamoylakylphosphonates as well as the diallyl
2-carbamoylalkylphosphonates of the prior art will, in this
disclosure, be collectively referred to as the "allyl
phosphonates."
While the use of aqueous solutions comprises the most economical
means of application for these allyl phosphonate flame retardants,
they may also, if desired, be applied to a normally flammable
substrate while dissolved in any of the organic solvents commonly
used in the solvent finishing of textiles including, for example,
trichloroethylene, dischloroethane, trichloroethane,
perchloroethylene, methylene chloride, etc. and mixtures thereof.
The solutions, either aqueous or organic solvent, containing one or
more of the selected allyl phosphonates may be applied to textiles
or other substrates by the use of any desired procedure. It is
merely necessary to have the diallyl phosphonate evenly absorbed
throughout the mass of the textile, or other substrate, and/or to
apply it to at least one surface thereof by means of any convenient
procedure. Thus, it may be applied by being sprayed onto one or
both surfaces of the substrate or, as is more frequently the case,
the substrate may be passed or padded through the solution while
the latter is being held in a tank or other suitable container.
Such a process is commonly referred to as a "padding technique"
with the solution being referred to as a "padding bath" or "padding
solution."
The concentration of the allyl phosphonate within the padding bath,
or other applicable solution, will be dependent upon a member of
factors including, in the case of textile substrates, the nature of
the fibers which comprise the textile, the weight and weave of the
textile, the degree of flameproofing that is desired in the
finished textile, as well as other technical and economic
considerations known and understood by those skilled in the art.
However, it is generally desirable that the padding bath should
contain an amount of the phosphonate such that when the wet uptake
is reduced to a dry deposit upon the textile or other substrate,
the treated substrate will contain from about 5 to 40 percent of
the allyl phosphonate, as based upon the dry weight of the
substrate. Again, it is to be stressed that the latter limits are
merely illustrative and may be varied so as to provide a finished
article having any desired degree of flame retardancy.
The thus applied allyl phosphonate may be cured in the wet state or
it may be completely or, most preferably, partially dried before
curing. The mode of curing in accordance with the process of the
invention involves the use of a free radical initiated reaction in
order to induce the double bonds, i.e. the ethylenic unsaturation,
of the allyl groups present in these compounds to polymerize
intermolecularly so as to form a crosslinked, insoluble resin in
and/or on the individual fibers, or other structural elements,
which comprise the textile or other substrate.
Free radical initiation of the desired polymerization reaction may
be induced either by the use of those chemical catalysts known as
free radical initiators or by the use of the actinic radiation.
Suitable free radical catalysts encompass peroxygen compounds,
which may be used as part of a so-called redox system which contain
a chemical reducing agent in addition to the peroxygen compound,
and azo compounds. Examples of suitable peroxygen catalyst are
hydrogen peroxide, which is often used in conjunction with ferrous
salts; ammonium, sodium or potassium persulfate; t-butyl
hydroperoxide; benzoyl peroxide; lauroyl peroxide; dicumyl
peroxide; cumene hydroperoxide; t-butyl peroxypivalate; methyl
ethyl ketone peroxide; caprylyl peroxide and acetyl peroxide.
Examples of suitable azo catalysts include azobisisobutyronitrile
and azobisisovaleronitrile. These catalysts should be used in an
effective amount in the range of from about 0.01 to 5 percent, by
weight, of the allyl phosphonate flame retardant; the precise
amount required being dependent upon the tightness of the cure,
i.e. the degree of crosslinking, which is required as well as the
extent to which free radical, chain inhibiting substances such as
oxygen have been excluded from the system.
Actinic radiation encompasses high energy protons and other
particles capable of initiating free radical reactions including
ultraviolet light, x-rays, gamma rays, alpha rays, beta rays, i.e.
electron beam radiation, and plasma, i.e. highly ionized atoms in
the vapor state. A preferred source of actinic radiation involves
the use of an electron beam, i.e. beta radiation, since equipment
adaptable for textile and paper mill use is readily available and
is eminently suited for rapid, continuous processing. In any event,
regardless of the type of actinic radiation that is used, it should
be applied in an effective dosage in the range of from about 0.1-10
megarads; the exact dosage being dependent on the tightness of cure
required, the amount of inhibitors present and the geometry and
nature of the substrate.
Where a cure is induced by the use of a free radical catalyst, the
selected catalyst is generally activated by heating up to about
200.degree.C. but, preferably, in the range of from about
60.degree. to 165.degree.C. so as to minimize any thermal damage to
the substrate. Alternatively, the catalyst can be activated, even
at ambient temperatures, by applying a reducing agent to the
textile or other substrate either before or after applying the
flame retardant reagent and catalyst. Suitable reducing agents
include sulfur dioxide, ferrous salts, such as the halides and
sulfates, as well as sulfurous, phosphorous, or hypophosphorous
acids and their water soluble salts such, for example, as sodium
bisulfite, sodium phosphite and sodium hypophosphite. The catalyst
may also be activated by actinic radiation.
When actinic radiation is used, either along or in combination with
a free radical catalyst, it is only necessary to expose the
substrate to a beam from a radiation source. If desired, this can
be done at ambient temperature thus sparing the substrate from
thermal damage. The exposure can be conveniently conducted by
passing the substrate through the beam which may be produced, for
example, by a bank of ultraviolet lamps, corona-discharge points, a
cobalt-60 source, an X-ray source or an electron beam source.
Reasonably homogeneous radiation flux is desirable where an
electron beam is used, thus the beam can be transversely scanned at
a rapid rate across the substrate so as to evenly irradiate all
points thereon. If desired, a suitable mechanical arrangement of
rollers can be employed so that the substrate can be made to
repeatedly pass through the radiation field thereby facilitating
more complete use of the available radiation flux while also
obtaining more uniform irradiation.
The use of radiation initiation does not generally require the use
of a chemical activator. However, the efficiency of the radiation
can frequently be improved by use of such an activator. Suitable
activators for this purpose include ketones, such as acetone or
benzoin; polycyclic hydrocarbons, such as polyphenyl; and, azo
compounds such as azobisisobutyronitrile. Where an electron beam is
used, the application of about 0.1-10 megarads, at a voltage
sufficient to substantially penetrate the substrate to the depth to
which the flame retardant polymer is to be formed, generally
sufficies to effect the desired cure.
The resulting cure, or polymerization, of the allyl phosphonate
which is induced by either a catalyst and/or actinic radiation
generally takes place on the surface and within the body of the
fibers, or other structural elements, which comprise the substrate.
Moreover, in some cases the resulting polymer network may be
grafted, or chemically bonded, onto the fiber molecules of the
textile or other substrate. However, such grafting is not crucial
to the attainment of a durable, flame retardant finish.
The irradiation of the substrate is usually carried out subsequent
to the application of the allyl phosphonate although, in the case
of cellulosic fibers, which can be irradiated so as to form stable,
long lived free radical sites, the allyl compound can be applied
subsequent to irradiation whereupon it will proceed to cure.
The process of this invention may, if desired, include the use of
other free radical curable, i.e. polymerizable, comonomers along
with the selected allyl phosphonate as a means of achieving
variations in the properties of the resulting treated textiles.
Thus, suitable optional comonomers for use in conjunction with the
allyl phosphonates include:
1. Monomers containing an amide nitrogen such as acrylamide,
methacrylamide, N-methylolacrylamide, diacetonylacrylamide,
methylenebisacrylamide, triacrylolhexahydrotriazine,
N-vinylpyrrolidone and cellulose-grafted N-methylolacrylamide, the
use of the latter monomer being disclosed in U.S. Pat. No.
3,434,161. The use of these amide nitrogen containing comonomers at
a concentration of about 0.1-6 moles per mole of the allyl
phosphonate, permits a more economical finish, particularly with
cellulosic fibers, since less of the more costly phosphonate
monomer needs to be used in order to achieve a given level of flame
retardancy.
2. Monomers containing more than one polymerizable double bond
such, for example, as the polyol polyacrylates or methacrylates,
the glycol diacrylates, the glycol dimethacrylates,
methylenebisacrylamide, triacryloylhexahydrotriazine,
triallylphosphonate, diallyl allylphosphonate and triallyl
cyanurate. By using this class of comonomers, the crosslink density
of the resulting finish can be increased thereby enhancing its
durability with respect to wear and laundering.
3. Monomers contributing to flame retardancy, i.e. monomers having
phosphorus, bromine or chlorine atoms in their molecules including,
for example, vinyl and vinylidene halides such as vinyl chloride,
vinyl bromide, vinylidene chloride, vinylidene bromide and
vinylidene chlorobromide; chloroprene; triallyl phosphate; diallyl
allylphosphonate; diallyl cyanoethylphosphonate; diallyl
carboxyethylphosphonate; dialkyl vinylphosphonates such as diethyl
vinylphosphonate, bis(2-chloroethyl) vinylphosphonate or its
polycondensation products; and, in general all of the unsaturated
phosphonate monomers disclosed in my copending applications Ser.
Nos. 23,493 (now abandoned) and 23,499 (now U.S. Pat. No.
3,695,925, issued Oct. 3, 1973) both filed Mar. 27, 1970. Other
suitable flame retardant comonomers are the compounds made by base
catalyzed addition of 1 to 2 moles of dialkyl phosphite and/or 1 to
3 moles of diallyl phosphite to the double bonds of
triacryloylhexahydrotriazine. When utilized in the process of this
invention, these optional comonomers should be present in the
system in a concentration of up to about 10 percent, by weight, of
the diallyl phosphonate.
It should be noted, at this point, that the use of the term
"crosslinked" in describing the cured, fire retardant resins
resulting from the polymerization of the selected allyl phosphonate
in the finishing process of this invention will indicate to those
skilled in the art that these resins possess a highly intermeshed,
three-dimensional configuration or network rather than a simple
linear or branched structure of the type found in non-crosslinked
copolymers. Thus, such crosslinked polymers may be further
characterized by the fact that they will not lose more than about
20 percent of their total weight upon being extracted with methanol
in a Soxlet extractor. Moreover, as used in this disclosure, the
term "fire retardant" is intended to refer to that particular
property of a material which provides it with a degree of
resistance to ignition and burning. Thus, a fire or flame retardant
textile, paper or other solid substrate is one which has a low
level of flammability and flame spread. This property may be
conveniently evaluated by means of any of the standard flame
retardancy tests.
In contrast to the known diallyl 2-cyanoethyl phosphonate finishes,
pre-polymerization of the above described allyl phosphonates is not
necessary in the process of this invention. However, it is within
the purview of this process to permit such pre-polymerization for
the purpose of permitting extremely rapid cures of the flame
retardant finish on the textile or other substrate since some of
the polymer links will have been formed prior to its application to
the cloth. Advantageously, pre-polymers of these allyl phosphonates
can be prepared without losing the solubility in water which is
displayed by the unpolymerized phosphonates by simply limiting the
extent of the pre-polymerization so that it does not exceed the gel
point. With any given catalyst system, this can be readily
determined by a preliminary experiment to define the required
heating time and temperature prior to preparing the treating bath
for the full-scale finishing operation. However, in general, in
preparing these pre-polyomers it may be noted that the solution of
the allyl phosphonate should be heated until its viscosity has
increased by about 50-500 percent with heating being halted at the
first appearance of cloudiness. Moreover, it is to be noted that
the novel tetraallyl phosphonates of this invention have an
advantage over the diallyl posphonates since they act like
pre-polymers in the sense of being able to cure extremely rapidly
to a thermoset condition using amounts of initiator or of radiation
which are only about half (or less) of those required with the
diallyl compounds.
The process of this invention is compatible with a wide variety of
other textile finishing operations which can be carried out prior,
simultaneous with, or subsequent to the process of the invention.
These other operations include application of durable press,
softening, antistatic, abrasion resistance, water-repellent,
soil-release, and antimicrobial finishes, as well as bleaching,
dyeing, printing, flocking, and texturing.
Thus, the finishing formulations of the invention may also
optionally contain other types of ingredients known in the textile
finishing art. For example, water and soil repellents, optical
brighteners and colorants, softening agents such as polyethylene
emulsions, hand-modifying agents, buffering agents, pH-controlling
agents which may be acidic or basic, emulsified waxes, chlorinated
paraffins, polyvinyl chloride, polyvinylidene chloride, homo- and
copolymers of the alkyl acrylates and other resinous finishing
agents may be added in conjunction with the finishing agents of the
invention. And, where an extremely high degree of flame retardance
is required, it is also possible to employ systems containing
antimony oxide, a resinous binder, particularly one containing
chloride such as a chlorinated paraffin of polyvinyl chloride,
along with the allyl phosphonates required in the process of this
invention. Moreover, in treating wood and paper substrates, the
fire retardant finishes of this invention may be applied along with
and as part of an aminoplastic binder resin. And, when used for
finishing paper, these allyl phosphonates can be used in
conjunction with any of the various adhesives, sizes, wet strength
additives and other materials which are ordinarily employed in the
paper finishing art.
A hitherto unmentioned advantage of the process of this invention
over prior art flame retardant finishing process resides in the
fact that the application of the finish does not depend upon the
presence in the system of compounds containing readily broken
--N--CH.sub.2 -- or --O--CH.sub.2 -- linkages, thereby permitting
high levels of durability to be achieved in the resulting flame
retardant finishes, including durability to acidic "laundry sours"
which strip the prior art aminoplast finishes from the textile.
All types of textiles may be treated by means of the process of
this invention so as to provide them with durable, fire retardant
finishes. Thus, one may treat textiles derived from natural fibers
such as cotton, wool, silk, sisal, jute, hemp and linen, wood and
from synthetic fibers including nylon and other polyamides;
polyolefins such as polypropylene; polyesters such as polyethylene
terephthalate; cellulosics such as rayon, cellulose acetate and
triacetate; fiber glass (which is flammable when coated with
organic sizing agents); acrylics and modacrylics, i.e. fibers based
on acrylonitrile copolymers; saran fibers, i.e. fibers based on
vinylidene chloride copolymers; rubber based fibers; spandex
fibers, i.e. fibers based on a segmented polyurethane; vinal
fibers, i.e. fibers based on vinyl alcohol copolymers; vinyon
fibers, i.e. fibers based on vinyl chloride copolymers and,
metallic fibers. Textiles derived from blends of any of the above
listed natural and/or synthetic fibers may also be treated by means
of the process of this invention.
As used in this disclosure, the term "textile" or "textiles" is
meant to encompass woven or knitted fabrics as well as non-woven
fabrics which consist of continuous or discontinuous fibers bonded
so as to form a fabric by mechanical entanglement, thermal
interfiber bonding or by use of adhesive or bonding substances.
Such non-woven fabrics may contain a certain percentage, up to 100
percent, of wood pulp as well as conventional textile fibers in
which case part of the bonding process is achieved by means of
hydrogen bonding between the cellulosic pulp fibers. In non-woven
fabrics, the finishing agents of this invention can serve not only
as flame retardant finishes but can also contribute to the
interfiber bonding mechanism by serving as all or part of the
adhesive or bonding resin component. This dual role can also be
played by the finishing agents of this invention in fabric
laminates where the finishing agent can at the same time serve as
the interlaminar bonding agent and as the flame retardant. In both
of these systems, i.e. non-woven fabrics and laminated fabrics, the
finishing agents of this invention can also be blended with the
usual bonding agents such, for example, as acrylic emulsion
polymers, vinyl acetate homo- and copolymer emulsions,
styrenebutadiene rubber emulsions, urethane resin emulsions,
polyvinyl chloride emulsions, vinyl chloride-alkyl acrylate
copolymer emulsions polyacrylates modified by vinylcarboxylic acid
comonomers and the like.
It should also be noted, at this point, that in addition to being
used to provide flame retardant finishes for textiles, the above
described allyl phosphonates can also be employed for the
flameproofing of a wide variety of polymeric substrates such as
cellulose in the form of paper, wood, plywood, chipboard, jute,
batting and the like; urethane foams, coatings, and elastomers;
aminoplast resins and phenolic resins as well as their composites
with paper, wood flour and the like; alkyd coatings and molding
resins; and, paints and varnishes derived from natural or synthetic
resins.
The following examples will further illustrate the embodiment of
this invention. In these examples all parts given are by weight
unless otherwise noted.
EXAMPLE I
This example illustrates the preparation of diallyl
2-carbamoylethylphosphonate, ##SPC3##
To a stirred mixture of 162 g. of diallyl phosphonate and 71 g. of
acrylamide, there is slowly added a 4 percent, by weight, solution
of sodium in allyl alcohol. The mixture is cooled during and
subsequent to its preparation so as to maintain its temperature
below 65.degree. C. When no further temperature rise occurs, the
reaction mixture proceeds to form a solid, m.p. 51.2.degree.C., the
infra-red spectrum of which shows no P-H band. The nuclear magnetic
resonance spectrum shows protons characteristic of P--CH.sub.2
CH.sub.2 C(=0)-- (.delta. 2.33), CH`--O--P (.delta. 4.5), CH.sub.1
=CH-- (.delta. 5.6) and NH.sub.2 (two NH's) in the correct area
ratio of 4:4:6:2.
EXAMPLE 2
This example illustrates the preparation of a flame retardant
textile finish by means of the process of this invention.
An aqueous padding bath is prepared which contains 20 percent, by
weight, of the diallyl 2-carbamoylethylphosphonate whose
preparation is described in Example 1 along with 0.6 percent, by
weight, of ammonium persulfate as a catalyst. Cotton and dacron,
i.e. polyethylene terephthalate, cloths are padded therein, dried
at room temperature to a slight degree of moisture retention and
thereupon cured by pressing for 3 minutes, at 330.degree.F., in a
steam heated press The thus treated cloths are then washed in
water, dried and analyzed for phosphorus by means of X-ray
fluorescence. They are then subjected to an accelerated laundering
procedure by being boiled for 3 hours in a solution containing 0.5
percent, by weight, of soap and 0.2 percent, by weight, of sodium
carbonate. The thus treated cloths are then reanalyzed and their
flame retardancy evaluated by means of the limiting oxygen index
(LOI) method as described in ASTM D-2863. In brief, this procedure
directly relates flame retardancy to a measurement of the minimum
percentage concentration of oxygen in a oxygen:nitrogen mixture
which permits the sample to burn; the LOI being calculated as
follows:
LOI = [O.sub.2 ]/[O.sub.2 ] + [N.sub.2 ] X 100
Thus, a higher LOI is indicative of a higher degree of flame
retardancy.
The following table presents the results of these evaluations.
Fabric % P Before Soap-Soda Wash % P After Soap-Soda Wash LOI
______________________________________ Cotton 1.1 1.1 24.8 Dacron
0.8 0.7 24.5 Untreated Cotton* -- -- 18.4 Untreated Dacron * -- --
20.8 ______________________________________ * Control
These results show excellent durability to laundering and good
flame retardancy on the part of fabrics treated with the flame
retardant finish of this invention. Moreover, the thus treated
cloths exhibit a good "hand," good tear strength as well as a
retention of their original white color.
EXAMPLE 3
This example again illustrates the preparation of a flame retardant
textile finish by means of the process of this invention which, in
this case, utilizes an actinic radiation induced cure. It also
provides a comparison with the use of diallyl
2-cyanoethylphosphonate.
A padding bath is prepared by dissolving 20 parts, by weight, of
diallyl 2-carbamoylethylphosphonate in 79 parts of water which also
contains 1 part, by weight, of octyl phenoxy polyethoxy ethanol as
a wetting agent. For comparative purposes, a padding bath is
prepared containing 79 parts of diallyl 2-cyanoethylphosphonate, 1
part of octyl phenoxypolyethylene ethanol and, because of the
insolubility of the cyanoethyl phosphonate in water, 15 percent, by
weight, of methanol is also included. An 8 ounce cotton cloth is
padded in each of these baths to about a 70 percent, by weight, wet
add-on. These cloths are then dried to a slightly moist condition
and exposed to 4 megarads of electron beam radiation at 1.5 Mev.
The flame retardancy of the thus treated cloths is then evaluated
by means of the LOI procedure both before and after 5 detergent
launderings.
______________________________________ Fire Retardant % Dry Add-on
LOI Before Washing LOI After Washing
______________________________________ diallyl 2-carbamoylethyl
phosphonate 12.79 25 24 diallyl 2-cyanoethyl phosphonate 11.83 24
19 Control * -- 18 -- ______________________________________ *
Untreated Cotton
Thus, the above given data reveal that the carbamoyl compound
required for use in the process of this invention provides durable,
flame retardant properties in the treated fabric whereas the finish
derived from the cyanoethyl compound is substantially all removed
by laundering.
In another comparison of intrinsic flame retardant properties,
aside from the question of durability, the carbamoyl and cyano
compounds are again compared at varying levels of add-on on 3.2 oz.
cotton cloths which are treated in the manner described
hereinabove. The following table provides the results of this
comparison.
______________________________________ Fire Retardant % Dry Add-on
LOI Before Washing ______________________________________ diallyl
2-carbamoylethyl phosphonate 10 23.9 Do. 15 26.0 Do. 20 27.5 Do. 25
28.7 diallyl 2-cyanoethylphosphonate 10 23.5 Do. 15 24.8 Do. 20
25.6 Do. 25 26.2 ______________________________________
The above data clearly indicate that at all add-on levels, the
finishes of this invention display superior fire retardancy when
compared with the finishes derived from the cyanoethyl phosphonate
compound.
EXAMPLE 4
This example illustrates the preparation of
N,N'-methylenebis(diallyl- 2-carbamoylethylphosphonate), i.e.
##SPC4##
To a slurry of 154 gms. of N,N'-methylenebisacrylamide and 324 gms.
of diallyl phosphonate in 800 ml. of methylene chloride there is
added, with stirring, 2.9 gms. of sodium methylate. The reaction
mixture spontaneously boils and methylene chloride is allowed to
distill off until the reaction subsides. The resulting reaction
mixture is homogeneous except for trace solids which are removed by
filtration. The infrared spectrum of the filtrate shows no
remaining P-H compound. The solution is then stripped to
50.degree.C. under vacuum leaving a substantially quantitative
yield of the product as a yellowish syrup, n.sup.D.sub. 23 1.4998
which is completely soluble in water.
- Analysis: Calcd. for C.sub.19 H.sub.32 O.sub.8 P.sub.2 N.sub.2
:13.0 % P
Found: 12.9% P
The above given structure is confirmed by nmr spectroscopy. When
this monomer is directly exposed to the radiation from a mercury
vapor lamp for a period of several hours, it cures to form a clear,
solid, extremely hard polymer having a Barcol hardness value of 50.
This polymer also has good impact strength as demonstrated by the
fact that a 1/8 .times. 2 inch diameter plaque survives several 40
ft. falls without shattering.
In a repetition of tha above described procedure,
N,N'-methylenebismethacrylamide is, in this instance, substituted
for N,N-methylenebisacrylamide thereby yielding
N,N'-methylenebis(diallyl 2-carbamoylisopropylphosphonate) as the
product of the reaction in the form of a viscous syrup.
EXAMPLE 5
This example again illustrates the preparation of a flame retardant
textile finish by means of the process of this invention.
Three padding baths are prepared whose respective compositions, in
parts by weight, are shown in the following table. Cotton cloth
having a weight of 32 oz/yd.sup.2 is padded in each of these baths,
passed through a wringer, dried at room temperature for 15 minutes
and then cured between heated rolls at 280.degree.-300.degree.F.
for 5 minutes. The LOI of each cloth before and after 5 detergent
washes is then determined and these results are also shown in the
table.
______________________________________ Padding Bath A B C
______________________________________ N,N'-methylenebis (diallyl
2-carbamoylethylphosphonate) 35 25 15 Acrylamide (comonomer) -- 10
20 Ammonium persulfate (catalyst) 0.5 0.5 0.5 Octyl
phenoxypolyethylene ethanol (wetting agent) 0.4 0.4 0.4 Water 64.1
64.1 64.1 Dry add-on (%) 26.3 25.2 23.6 LOI before washing 30.69
30.27 27.38 LOI after 5 detergent washings 24.23 25.74 24.21
______________________________________
Since the untreated cloth has an LOI of only 18, it is seen that
the process of this invention imparts a substantial degree of
durable flame retardancy.
EXAMPLE 6
This example illustrates the flame retarding of paper by means of
the process of this invention.
Weighed pieces of paper are impregnated with each of the below
described solutions:
(A.sub.10) diallyl 2-carbamoylethylphosphonate 10% by wt.
(aqueous)
(A.sub.20) diallyl 2-carbamoylethylphosphonate 20% by wt.
(aqueous)
(A.sub.40) diallyl 2-carbamoylethylphosphonate 40% by wt.
(aqueous)
(B.sub.10) diallyl 2-cyanoethylphosphonate 10% by wt.
(alcoholic)
(B.sub.20) diallyl 2-cyanoethylphosphonate 20% by wt.
(alcholic)
(B.sub.40) diallyl 2-cyanoethylphosphonate 40% by wt.
(alcholic)
(C.sub.10) N,N'-methylenebis(diallyl) 2-carbamoylethylphosphonate)
10% by wt. (aqueous)
(C.sub.20) N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate)
20% by wt. (aqueous)
(C.sub.40) N,N'-methylenebis(diallyl 2-carbamoylethylphosphonate)
40% by wt. (aqueous)
In each case, the paper is saturated to a wet-uptake of
approximately 200 percent, by weight. The thus treated papers are
dried for 15 minutes in an oven set at 70.degree. C. and then
irradiated by exposure to a 400-watt high pressure mercury arc lamp
for a period of 24 hours. The dry add-ons, i.e. the weight of the
treated paper less its original weight .times.0 100/original
weight, are determined both before and after a 15 minute wash with
running water, and the flame retardancy of each sample is evaluated
both before and after the water wash. The flame retardancy of these
sheets is expressed on the following scale:
+++ (excellent retardancy) = self-extinguishing when its lower edge
is ignited while the strip is suspended in the vertical
position;
++ (good retardancy) = self-extinguishing when its lower edge is
ignited while suspended at an inclination of 45.degree. ;
+ (slight retardancy) = self-extinguishing where one end is ignited
while the strip is suspended in a horizontal position; and
- (not self-extinguishing in any position).
The results of this evaluation are presented in the following
table:
______________________________________ Dry Add-on (%) Flame
Retardance - Treating Solution Before Washing After Washing Before
Washing After Washing ----------------------hz,1/32 A.sub.10 16.2
2.1 ++ --/ -A.sub.20 30.3 14.1 +30 30 -- A.sub.40 62.5 42.4 ) -) -)
+ B.sub.10 3.5 0.9 -- -- B.sub.20 7.4 1.0 + -- B.sub.40 10.5 1.9 ++
-- C.sub.10 16.1 9.6 ++ + C.sub.20 37.1 22.1 +++ ++ C.sub.40 72.2
70.5 +++ ) -) -) ______________________________________
These results reveal that the finish derived from diallyl
@cyanoethylphosphonate is substantially lost during the curing
whereas the finishes of this invention are retained. It is also
seen that the novel tetraallyl compound provides a finish which is
exceedingly durable to water washing.
EXAMPLE 7
This example illustrates the preparation of a thermoset polymer
composition from the diallyl 2-carbamoylethylphosphonate whose
preparation is described in Example 1.
An aqueous solution containing 30 percent, by weight, of diallyl
2-carbamoylethylphosponate and 2 percent, by weight, of ammonium
persulfate is gradually warmed to within the range of
60.degree.-80.degree.C. During this warming period, the solution
forms a viscous pre-polymer. A portion of this pre-polymer is
removed and is used as a textile finishing agent which, after being
applied to the surface of a fabric, is cured by heating the thus
treated fabric so as to yield a water insoluble, flame retardant
finish. Prolonged heating of the balance of the pre-polymer
solution causes it to gel and thereafter a white, odorless water
insoluble polymer is precipitated. This polymeric product is then
dried and used as a flame retardant additive for flammable
polymers.
Variations may be made in proportions, procedures and materals
without departing from the scope of this invention as defined in
the following claims.
* * * * *