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Патент USA US2403465

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Patented July 9, 1946
/ 2,403,465
UNITED STATES PATENT OFFICE
2,403,485
TREATMENT OF BYDROXYL-CONTAINING
INTERPOLYMERS OF ETHYLENE
Donald Cargill Pease, Wilmington, Deb, assign
or to E. I. du Pont de Nemours 8: Company,
Wilmington, M, a corporation of Delaware
No Drawing. étpplicatlon69.460
December 18, 1942,
erialNo.4
(CL 260—42)
11 Claims.
1
This invention relates to polymeric materials
and more particularly to the treatment of hy
drolyzed interpolymers of ethylene and vinyl com
pounds containing organic .groups hydrolyzable
to hydroxyl groups whereby to term polymeric
materials having generally improved physical
characteristics.
2
monium persulfate or benzoyl peroxide at tom-1
peratures generally above 60° to ‘75° C. After sev
eral hours the polymer is taken out of the reac
tion vessel and unreacted vinyl acetate is steam
distilled off. Hydrolysis of these polyesters is car
ried out by dissolving them in alcohol or a tolu
ene- or benzene-alcohol mixture, and adding an
alcoholic solution of sodium or potassium hydrox
ide. Systems containing a substantial amount 01'
class of ?lm- and ?lament-forming polymeric
l0 water are also useful for the hydrolysis. After
materials.
hydrolysis has proceeded to the desired extent.
Another object is to provide a new class of poly
the solvents are steam distilled and the residual
meric materials derived from hydrolyzed inter
polymer washed and dried.
polymers oi’ ethylene and a vinyl compound con
The molar ratio of ethylene to vinyl acetate in
taining organic groups hydrolyzable to hydroxyl
interpolymer must be greater than 139 to
groups, said polymeric materials having higher 15 the
satisfy the requirement that less than 45% of the
melting points, lower water-sensitivity, lower sol
carbon atoms of the polymer chain be attached
ubility in organic solvents and generally improved _
to hydroxyl groups and organic groups hydrolyz
physical characteristics over the hydrolyzed inter
able to hydroxyl groups. The preferred range of
polymers from which, they are derived.
ratios is from 5:1 to 1:3, corresponding to
A further‘ object is to treat hydrolyzed inter 20 mole
from
8‘/:;% to 3'7%% of the carbon atoms at
polymers oi: ethylene and a vinyl organic ester to
tached to hydroxyl groups.
increase the melting point, to decrease the water
For most purposes it is desirable to use a prod—
sensitivity, to decrease the solubility, and to im
not that is hydrolyzed to the extent of (lo-100%.
prove the properties thereof generally.
In the event that the ultimate use requires a high
These and other objects will more clearly ap 25 degree of pliability, a product hydrolyzed about
An object of this invention is to provide a new
pear hereinafter.
_,
The above objects are accomplished by my in
vention which, brie?y stated, comprises reacting
, 75-85% is preferred, since the residual ester
groups provide a relatively permanent plastlcizing
action. On the other hand, for a use demanding
hydrolyzed interpolymers of ethylene and a vinyl 80 an
ultimately higher stiffness and/or tensile prop
organic compound in which less than 45% of the
erties, it is recommended that the polyesters be
carbon atoms of the polymer chain are attached
hydrolyzed 95-10095.
to groups from the class consisting of hydroxyl
The compounds characterized by having plu
groups and organic groups hydrolyzable to hy
rality of methylene groups, each of which isat
droxyl groups (i. e., ester, ether, and acetal
tached to nitrogen and oxygen, and hereinafter
groups), with compounds having a plurality of 35 termed
"reactive modifying agent,” are repre
methylene groups each of which is attached to ni
sented by the following examples: dimethylolurea
trogen and oxygen.
and its various others such as N,N'-bis-(meth
The hydrolyzed polymer preferred in the prac-v
oxymethyl) urea, ‘the aldehyde condensation
tice of the present invention is that formed by_ 40 products of triazine with at least two methylene
the hydroylsis of the interpolymer of ethylene
groups, each of which is attached to nitrogen and
with an organic ester such as vinyl acetate, and
oxygen, such as trimethylol melamine and the
the invention will be further illustrated with spe
alkyl others of trimethylol melamine, poly-N
ciiic reference to this interpolymer although it is
methylol derivatives of such polyamides as suc
to be understood that my invention is applicable 45 cinamide and adipamide, and monocyclic ureas
as well to the treatment of all hydroxyiated inter
having on each of the urea nitrogens a substitu
polymers of ethylene and vinyl compounds where
ent of the formula --CH2OR such as N,N'-bis
in less than 45% ot the carbon atoms or the poly- .
mer chain are attached to hydroxyl groups and
(methoxymethy!) uron.
While amounts up to
50% by weight, based‘ on the weight of the hy
groups hydrolyzable to hydroxyl groups, whether
the interpolymer is formed from vinyl organic 50 drolyzed interpolymer, of these compounds give
substantial modi?cation of the hydroxyl-contain
esters, ethers or acetals, or other suitable inter
ing polymer, I prefer to use from about 0.1% to
mediates.
- about 30% by weight of the reactive modifying
The polymerization oi’ the monomeric ethylene
agent.
and vinyl acetate can be carried out in aqueous
In the preferred practice of the invention the
emulsion in the presence of catalysts such as am 55
3
hydrolyzed inter-polymer. e. g. hydrolyzed ethyl
ene-vinyl acetate interpolymer, and the reactive
modifying agent, together with a suitable oon
densation catalyst such as hydrochloric or tolu
enesulfonic acid, are intimately associated in a
volatile organic solvent medium. The resulting
composition is then cast into ?lm or converted
into any other desired form by a suitable casting.
extrusion, or molding operation carried out at
4
,?lmwasbakedunderaninfraredlampiorti
crack of —10' C. Another portion of the cast
hour. It still remained insoluble after 10 minutes
in boiling toluene/ethanol (1:1) mixture while
control ?lm dissolved in this hot solvent mixture
in less than one minute.
Example II
A hydrolyzed ethylene-vinyl acetate interpoly
the lowest possible practical working tempera 10 mer having a mole ratio of 2.9: 1, 83% hydrolyzed
ture. Thereafter the organic solvent is removed
(11% of the carbon atoms of the polymer chain
and the treatment is completed by subjecting the
attached to hydroxyl groups and 2% attached to
solvent-free composition to temperatures oi i'rom
MCtOXY groups) is pressed into ?lms at 150° C.
70° to 200° C. for a period of time su?icient to
The ?lm is soaked in a solution composed 0! 95
produce a high-melting. insoluble product, usual 15 parts of dioxane. 5 parts of N,N'-bis(methoxy
ly from about 1 to 3 hours.
methyDuron and 0.05 part 01’ toluene suli'onic
The following examples further illustrate the
acid for 15 hours at 25° C. The dried ?lm is
invention. Parts are by weight, and the several
baked 2 hours at 70° C. After one month at 25°
terms and tests therein employed are de?ned as
C., it is found that the melting point is above
i’ollows:
20 300° C. The treated ?lm has a. tenacity of 3000
"Cold crack temperature" is determined by ?t
lbs/sq. in. with 200% elongation, and a pliability
ting a sample of ?lm approximately 3/4" x 2" in
of 110. Films of the same composition that had
the open jaws oi’ a wooden test tube holder and
not been chemically altered by reaction with N,N'
immersing in a cooling bath of known tempera
bis-(methoxymethylluron have a tenacity of
ture. After one minute a trigger is released, 25 3500 lbs/sq. in. with 400% elongation and a
melting point‘ 01' 98° 0.
causing the jaws oi’ the holder to strike sharply
on a 180° fold in the sample. The temperature
Example III
at which the ?rst perceptible break is made in
Ten parts of a completely hydrolyzed ethylene
the sample is termed the cold crack temperature.
“Melting point" is the temperature at which a 30 vinyl acetate interpolymer, having a mole ratio
?lm has zero tensile strength.
of 1:23 (35% 01' the carbon atoms in the polymer
chain attached to hydroxyl groups) is swollen at
“Mar temperature" is the temperature to which
the boiling .point of a mixture 01' toluene and
?lms need be heated in order to accept a perma
ethanol (1:1). One part of N,N'-bis(methoxy
nent imprint when pressed between the fore
?nger and thumb.
methylluron and 0.1 part of diethylmethylsul
"Tack temperature” is the temperature to
fonium iodide is added to this mixture with. stir
ring after which the solvents are allowed to evap
which a folded sample of ?lm need be heated
orate at room temperature. After drying at 00°
in order to stick together when pressed between
the thumb and fore?nger.
C. for 12 hours, the mixture of interpolymer,
"Sti?'ness" in lbs/sq. in. is equal to the stress 40 reactive agent and catalyst is heated in a mold
under 50 lbs/Sq. in. pressure for 2 hours at 185°
in pounds exerted upon a film at 1% elongation
C. The product has a melting point above 250°
divided by 1lion of the cross sectional area in
C., and at room temperature possesses a tough,
square inches of the unstretched ?lm.
rubbery character. Moldings oi’ the polymer
“Pliability” is 10‘ times the reciprocal of the
stiil'ness.
which have not undergone this reaction just de
"Flex durability” values are obtained on the
scribed have a melting point of 180° C. and are
Schiltknecht ?ex machine. The test consists in
quite stiff and brittle.
bending a 3" x 2" piece of ?lm into the form
N,N'-bis) methoxymetyl) uron as used in this re
Larger proportions of
action yield products having increased stiffness
of a cylinder and collapsing and restoring the
1
cylinder longitudinally at a rate of about 400 50 and high melting points.
cycles per minute. The sample is inspected pe
Example IV
riodically and the ?ex durability is taken as the
number of cycles necessary to crack the ?lm,
To a solution or 50 parts of hydrolyzed ethyl
ene-vinyl acetate'lnterpolymer having a mole ra
Example I
55 tio of 3.6:1, 90% hydrolyzed (9.9% of the carbon
atoms in the polymer chain attached to hydroxyl
To a solution of 15 parts of a hydrolyzed eth
ylene-vinyl acetate interpolymer having a mole
and 1.1% attached to alcetoxy groups), dissolved
ratio oi‘ 1:12, 87% hydrolyzed (22% of the car
in 300 parts of 1:1 toluene-ethanol mixture is
added 15 parts of N,N'-bis(methoxymethyl)urea.
bon atoms of the polymeric chain attached to
hydroxyl and 5% attached to acetoxy groups) in
Films are cast from this solution more easily than
those containing no modifying agent. After bak
85 parts of toluene-ethanol 1:1 mixture is added
2 parts of dimethylolurea and 0.035 part of
ing at 80°-85° C. for 1%‘ hours the ?lm modi?ed
hydrochloric acid. A ?lm is cast by ?owing this
solution on a smooth surface and evaporating
the solvent at room temperature. After baking
at 100° C. for 1 hour, the unsupported ?lm has a
with N,N'-bis(methoxymethyl)urea had armelt
ing point of 160° C., cold crack of —45° C., tack
temperature of 75° C., ‘and mar temperature of
70° C. The control unreacted ?lms have a melt
melting point of over 200° C., tack temperature
of 88° C., mar temperature of 114° C., cold crack
temperature of -13° C., tensile strength oi’ 3000
lb./sq. in. with 165% elongation, and a pliability
of 181. A control sample of ?lm unmodi?ed by
ing point of 93° C., cold crack temperature of
reaction with dimethylolurea has a tenacity or
Sixteen parts of a hydrolyzed ethylene-vinyl
-5° C., tack temperature of 73° C. and mar tem
perature of 90° C.
'
Example V
3300 lbs/sq. in. with elongation of 340%, pli
acetate inter-polymer having a mole ratio of 1.6:1,
ability of 121, melting point of 120° C., tack tem
83% hydrolyzed (16% of the carbon atoms 01' the
perature 76° C., mar temperature 99° C., and cold 75 polymer chain attached to hydroxyls and 3%
asoases
6
5
attaehedtoscetoxygroupsi,isdissolvedini00
tially higher melting points and decreased solu
parts ol toluene-ethanol 1:1 mixture, 0.48 part
of dimethylolurea is added to the solution with
stirring and Just belore ?lms are cast there is
added 0.02 part of ammonium dihydrogen phos
properties of hydrolysed ethylene-vinyl acetate
phate. Alter drying the like is baked one hour
at 100° C. The product of the chemical inter
action of dimethylolurea and the polyalcohol has
a tenacity of 8000 Ilia/sq. in. with an elongation
bility. It is quite unexpected that these modify
ing agents would so considerably enhance the
interpolymers that possess lewer reactive hy
dronl groups than polyvinyl alcohol when the
same modifying agents confer far less improve
ments upon the letter.
A variety of methods are available for ineor- '
of 250%, pliability oi 85. cold crack temperature
of -20° 0., and melting temperature over 200°
porating into the hydrolyzed ethylene-vinyl ace
tate lnterpolymers reactive modifying agents
C. A control iiim that has not been subjected
to this chemical reaction has a tensile strength
having a plurality of methylene groups, each of
which is attached to nitrogen and oxygen. The
reactive modifying agents can be added to solu
of 1000 lbs/sq. in. with 220% elongation, pliability
87, cold crack 0' 0., and a melting point of 80° C. 18 tions oi the hydrolyzed ethylene-vinyl acetate
interpolymers in organic solvents; the formed
Emmple VI objects of hydrolysed ethylene-vinyl acetate in
Eight parts 0! hydrolysed ethylene-vinyl ace- .
terpolymer can be treated directly with the agent
tate inter-polymer having a mole ratio of 3:1,
03% hydrolyzed (10% oi the carbon atoms in the
polymer chain attached to hydroxyls and 2.0%
attached to acetoxy groups). is dissolved in 50
parts of hot benzene-ethanol (1:1) mixture.
0.24 part of dimethylolurea is added, and lust )
previous to casting these ?lms 0.025 part of am
monium dihydrosen phosphate is added. Alter
the film has been dried at 75° C. for one day, it
has a tenacity o! 8800 lbs/sq. in. with 340%
elongation, pliability 01’ 01, melting .point ol 170°
0.. and a cold crack of —50° C. U
?lms are ?exed 1,500,000 times without failure.
Control lllms that have not been subjected to
chemical modi?cation have a tenacity of 3200
or solutions of it; or theagent can be worked
into the polymer on conventional milling or cal
endering equipment. Solvents that have been
used in_these procedures are usually permitted
to evaporate and ;he objects are baked at tem
peratures somewhat below those that cause their
deformation. Catalysts such as sullonic acids or
mineral acids or their acidic salts can be incor
porated with the modifying agent or can be added
later from the vapor phase or in any manner that
will not extract large quantities ol polymer or
modifying agent. By using temperatures that
accelerate the~reaction between the hydrolysed
lbs/sq. in. with 440% elongation, melting point
ethylene-vinyl acetate interpolymer and the mod
ifying agent for only short periods, it is possible
to soften the polymer suiiiciently to permit it to
of 95° 0.. and failed belore 200,000 ?exes.
be worked or to be formed into shapes that are
Example 'v‘n
.
A hydrolyzed ethylene-vinyl acetate interpoly
rendered relatively permanent by further heat
or catalytic treatment.
The melting point of objects made from un
mer having a mole ratio of 1.6:1. 00% hydrolyzed
treated hydrolyzed ethylene-vinyl acetate inter
(17% of the carbon atoms in the polymer chain 40 polymer having a mole ratio oi’ 3:1 is about 110° 0.
attached to hydroxyl groups and 2% attached
As the hydroxyl content of the polymer increases
to acetoxy groups) mills to a smooth sheet on
the‘ melting point increases, so that a completely
even speed rolls at 00° 0.. but the temperature
hydrolyzed polymer of ethylene-vinyl acetate
range is rather narrow as the polymer sticks badly .
having a mole ratio of 1:3 melts at about 170° C.
at higher temperatures. This material has a mar
The products of the reaction between hydrolysed
temperature oi‘ 70° C. and a cold crack tempera
ethylene-vinyl acetate interpolymers and the
ture of 5° C. A mixture of 10 parts of this poly
reactive modifying agents described in this inven
mer and 1 part of N.N'-bis(methoxymethyl)uron
tion frequently do not melt until temperatures
and1% ammonium chloride catalyst can be suc
over 200‘ C. have been attained and are in every
cessfully milled at 60° C. When this mixture is 50 instance substantially higher melting than the
calendered on a fabric at 80° C. and baked for
corresponding untreated polymer. The increase
’ one hour at 100° 0.. it is found to have a mar
in melting point will of course depend on the
‘ temperature of 150° C. and a cold crack of -20° C.
chemical composition ol the product as deter
It is to be understood, ol course. that the above
mined by the proportions of thereactants, i. e.
examples are lot purposesol illustration and that 55 polymer and reactive modifying agent, the con
the invention is not limited to the exact mate
ditions i'or chemical reaction. ethylene/vinyl
rials and conditions therein described but is sus
acetate ratio. and degree of hydrolysis.
ceptible rather to considerable variation.
Moisture absorption which normally increases
Thus, while the preferred mole ratio of ethylene
with increase in hydroxyl content in the poly
to vinyl acetate in the ethylene-vinyl acetate
meric material is greatly reduced by the treat
interpolymer lies within the range 0! 5:1 and 1:8
ments of this invention thus advantageously .
(Bl/3% to 37%% of the carbon atoms in the poly
yielding a product with physical properties less
mer chain attached to hydroxyl groups), for some
easily in?uenced by changes in humidity.
uses it is possible to secure sumcient modi?ca
The stillness ol the ?nal product can be ad
tion by the present chemical treatment to render 66., lusted by.the proportions of the modllying agents
polymers having a ratio of ethylene/vinyl acetate
used. Larger proportions of the agents ordinarily
0! 40:1 (1% of the carbon atoms of the polymer
lead to products with higher stillness. Substan
chain attached to hydroxyl groups or groups
tially completely hydrolyzed ethylene-vinyl ace
hydrolyzable to hydroxyls) , useful in certain ap
tate interpolymer having a mole ratio ol 8:1
plications. Furthermore. hydrolyzed ethylene 70 (12%% ot the carbon atoms in the polymer chain
vinyl acetate interpolymers having an ethylene]
are attached to hydroxyls) has a dry tenacity of
vinyl acetate ratio in the range of 1:3 to 1:0‘
about 3,000 lbs./sq. in. with 300% elongation and
(hydroxyls on 37%?!) t045% of the carbon atoms
a stillness of about 015x10‘ lbs/sq. in. at 00%
R. H. The stillness is unchanged or may even
in the polymer chain) respond to the treatment
0! this invention to yield products ol substan 76 be slightly decreased by about 1% by weight ol
8
drolyzed interpolymer of ethylene and vinyl ace
tate. in which hydrolyzed interpolymer from
8%% to 375/29,’, of the carbon atoms of the poly
the modifying agent while 10% of the same modi
fying agent usually doubles the stiffness. Both
tenacity and stiffness increase with hydroxyl con
tent so that by selecting the hydrolyzed ethyl
ene/vinyl acetate ratio of the unreacted polymer
and the quantity of modifying agent added, with
mer chain are attached to groups from the class
consisting of hydroxyl groups and acetate groups.
with a compound having a plurality of methylene
groups each of which is attached to nitrogen and
oxygen, whereby to form a substantially insolu
a view to what is ultimately desired in tenacity
and stiffness, it is possible to obtain useful prod
his product having a melting point substantially
nets with a considerable range in stiffness and
tenacity.
Substantially completely hydrolyzed
10 higher than that of said interpolymer.
ethylene-vinyl acetate interpolymer having a
mole ratio of 1:3 (Wt/2% of the carbon atoms in
the polymer chain attached to hydrcxyls) modi
?ed according to this invention has a tenacity of
about 6,000 lbs/sq. in. with 200% elongation and 15
3. A method which comprises reacting a hy
drolyzed interpolymer of ethylene and vinyl ace
tate, in which hydrolyzed interpolymer from
til/3% to 37%70 of the carbon atoms of the poly
a stiffness of 0.5-1.0X 108 lbs. /sq. in. at 50% rela
tive humidity.
For such uses as fabric coatings where high
pliability and low stiffness is desired, a 1:1 or
higher, e. g. 3:1, composition with small amounts
consisting of hydroxyl groups and acetate groups,
with a compound having a plurality of methylene
groups each of which is attached to nitrogen and
oxygen, in the presence of an acid condensation
catalyst, whereby to form a substantially insoluble
of modifying agent is recommended. The prod
ucts of reaction from the 1:3 compositioh and
larger amounts of the polyfunctional reagents
have higher stiffness and tenacity, rendering them
useful as unsupported objects to accept stresses 25
in longitudinal or transverse directions.
If the hydrolyzed ethylene-vinyl acetate inter
polymer containing the reactive modifying agent ,
and catalyst has not been given su?lcient heat
treatment to render it unworkable, it is possible 30
to add other reactive agents in a plurality of
after-treatments from solvents that do not re
move or react with substantial amounts of agents
previously added. The reaction can also be de
layed by withholding catalyst until desired op
erations have been completed. Catalyst can then
be added from the vapor phase by milling or by
solvents in a manner that will not necessarily
extract the desired ingredients from the, modi?ed
mer chain are attached to groups from the class
product having a melting point substantially
higher than that of said interpolymer.
4. A method which comprises intimately asso
ciating a hydrolyzed interpolymer of ethylene and
vinyl acetate, in which hydrolyzed interpolymer
,_ from 1% to less than 45% of the carbon atoms '
-of the polymer chain are attached to groups from
the .class consisting of hydroxyl-groups and ace
tate groups, with a compound having a plurality
of methylene groups each of which is attached to
nitrogen and oxygen, in an organic solvent me
dium, evaporating said solvent and heating the
solvent-free composition to a temperature of
from 70° C. to 200° 0., whereby to form a sub
stantially insoluble product having a melting
point substantially higher than that of said inter
polymer.
5. A product produced by the process of claim 1.
6. The method which comprises intimately as
polymer. Furthermore, there is usually su?lcient 40 sociating, in an organic solvent, from 0.1 to 30
parts by weight of dimethylolurea with 100 parts
time lag between the addition of the reactive in
by weight of a hydrolyzed interpolymer of ethyl
gredients tb the polymer and the ?nal setting to
ene and vinyl acetate, in which hydrolyzed inter
permit working the mixture on hot rolls and
polymer from lit/3% to 37% % of the carbon atoms
adding other agents. Other substances that do
not necessarily react with the polymer or the 45 of the polymer chain are attached to groups from
the class consisting of hydroxyl groups and ace
modifying agents such as dyes, pigments, sizes,
tate groups, at least 50% of said groups being
weighting materials, ?llers, and plasticizers such
hydroxyl groups, evaporating said solvent and
as dibutyl phthalate, tricresyl phosphate, and di_
heating the solvent-free composition at a tem
butoxyethyl sebacate, can also be added either at
perature within the range of from 70° C. to 200°
the time that the polymer is in solution or during
the period when it can be successfully Worked on
C., whereby to form a substantially insoluble
product having a melting point substantially
hot rolls.
Hydrolyzed ethylene-vinyl ester compound in
higher than that of said interpolymer.
terpolymers modi?ed by the chemical interaction
‘7. A product had according to the process of
with the reactive modifying agents herein dis
claim 6.
closed are useful in the manufacture of self
8. The method which comprises intimately as
sustaining film for wrapping and packaging,
sociating, in an organic solvent, from 0.1 to 30
sheeting, ?bers, tubing, ?laments, molding com
positions, rubber substitutes, coatings for fabrics
and wire, protective ?nishes, adhesives for ply
wood, paper, and textiles, bars and other unsup
ported massive objects, ribbons, etc.
I claim:
1. A method which comprises reacting a hy
drolyzed interpolymer of ethylene and vinyl ace
tate, in which‘ hydrolyzed interpolymer from 1%
to less than 45% of the carbon atoms of the poly
mer chain are attached to groups from the class
consisting of hydroxyl groups and acetate groups,
parts by weight of N,N'-bis (methoxymethyl) urea
with 100 parts by Weight of a hydrolyzed inter
60 polymer of ethylene and vinyl acetate, in which
hydrolyzed interpolymer from ill/5% to {WE/2%
of the carbon atoms of- the polymer chain are
attached to groups from the class consisting of
hydroxyl groups and acetate groups, at least 60%
of said groups being hydroxylgroups, evaporating
said solvent and heating the solvent-free com
position at a temperature within the range of
from 70°, C. to 200° 0., whereby to form a sub
stantially insoluble product having a melting
with a compound having a plurality of methylene 70 point substantially higher than that of said inter
polymer.
groups each of which is attached to nitrogen and
9. A product had according to the process of
oxygen, whereby to form a substantially insolu
claim 8.
ble product having a melting point substantially
higher than that of said interpolymer.
2. A method which comprises reacting a by
10. The method which comprises intimately as
76 sociating, in an organic solvent, from 0.1 to 30
2,403,486
9
parts by weight 0! an alkyl ether of trimethylol
melamine with 100 parts by weight of a hydro
lyzed inter-polymer of ethylene and vinyl acetate,
in which hydrolyzed interpolymer from ill/3% to
37%% oi.’ the carbon atoms of the polymer chain
are attached to groups from the class consisting
of hydroxyl groups and acetate groups. at least
60% of said groups being hydroxyl groups. evapo
rating said solvent and heating the solvent-free
10
composition at a temperature within the range of
from 70° C. to 200° 0., whereby to form a sub
stantially insoluble product having a melting
point substantially higher than that oi’ said inter
polymer.
11. A product had according to the process of
claim 10.
DONALD 0. PHASE.
Certi?cate of Correction
July 9, 1946.
Patent No. 2,403,465.
.
DONALD CARGILL PEASE
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered’patent requiring correction as follows: Column 8, line 47, claim 6, for “at
least 50% read at least 60%; and that the said Letters Patent should be read with‘
this correction therein that the same may conform to the record of the case in the
Patent Office.
Signed and sealed this 17th day of September, A. D. 1946.
[m]
LESLIE FRAZER,
First Assistant Gammissicnar of Patents.
2,403,486
9
parts by weight 0! an alkyl ether of trimethylol
melamine with 100 parts by weight of a hydro
lyzed inter-polymer of ethylene and vinyl acetate,
in which hydrolyzed interpolymer from ill/3% to
37%% oi.’ the carbon atoms of the polymer chain
are attached to groups from the class consisting
of hydroxyl groups and acetate groups. at least
60% of said groups being hydroxyl groups. evapo
rating said solvent and heating the solvent-free
10
composition at a temperature within the range of
from 70° C. to 200° 0., whereby to form a sub
stantially insoluble product having a melting
point substantially higher than that oi’ said inter
polymer.
11. A product had according to the process of
claim 10.
DONALD 0. PHASE.
Certi?cate of Correction
July 9, 1946.
Patent No. 2,403,465.
.
DONALD CARGILL PEASE
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered’patent requiring correction as follows: Column 8, line 47, claim 6, for “at
least 50% read at least 60%; and that the said Letters Patent should be read with‘
this correction therein that the same may conform to the record of the case in the
Patent Office.
Signed and sealed this 17th day of September, A. D. 1946.
[m]
LESLIE FRAZER,
First Assistant Gammissicnar of Patents.
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