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Патент USA US2133689

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Patented Oct. Ida-19348
_
2,133,689
UNITEDv STATES PATENT OFFICE ‘
_ aiaassa
UREA ALDEHYDE MOLDING GOMPOSITIGNS
ggSNi‘I‘AINING A LATENT CURING CATA
Carieton Ellis; Montclair, N. 1., minor, .by means
cuts, to Piaskon Company Incorporated.
New York, N. Y.. a corporation oi’ Delaware
No Drawinr. Application April 30, 1987, '
.
Serial No. 139,9“
'
9Claims.(CL106-—22)‘
'.
This invention relates to ureaealdehyde mold- because of the possibility of toxic substances
ins compositions containing a curing catalyst of
the latent type. and to the process of making and
_ using the same.
5‘
_
',
By a latent catalyst I mean a substance of
being introduced.
"
According to H. M. Dawson and M. B. Dyson
(J. C. S., 1933, 49 and 1133) and. other investi
gators, such salts decompose to give the metallic 5
811011 type as de?ned in my U. 8. Patent 1,905,999,
halogenate and the corresponding hydroiiy car-
that is,,one which is active only when a given
boxylic 361d.' It is probable that the curins
.
temperature is reached. such a curing agent I action oi such substances is due to the ‘free acid
should preferably release an acid only at a tem1o perature near that at which hot pressing is ordinarily carried out, namely in the neighborhood
of 150° C, A latent catalyst is important in that
it allows a composition to be prepared which may
be stored for long periods before use and when
15 the composition is placed in a hot die and subjected to pressure, the “cure" of the composition,
\ i. e. polymerization .and condensation thereof, is
facilitated by the acid released by said catalyst.
Other prerequisites of such a catalyst are: (i) it
20 should be stable over a long period of time and
at temperatures below the temperature oi-hot
liberated, but partial hydrolysis of the metallic
salt lay-product or the reaction may aid the catal- 1o
ysis. In the case of iii-halogenated acids, the
reaction .may take a diiierent course. The above
theory 18 o?el‘ed'?s 8n explanation only. and I do
not wish to be limited thereby; I have deter
mined. however, that if crystalline sodium mono- 15
chloracetate is heated to a temper?tum Biwh 88
‘used in 11101611118. in Mid mummi?ed ‘which 8"”
a positive test with wet'litmus paper but gives a
negative test with silver nitrate, thus proving
that an acid is liberated which is not hydrogen 20
chloride.
'
’
‘
-
Dressing: (2) it should be substantially neutral '
In making '5 urea- resln molding 00111110831011
before being broken down by the heat and pres- I may react 1 mole oi’ urea or equivalent sub
sure of molding; (3-) it should be colorless, and stance with 1 to 2 moles, preferably-1.5 moles, of
25 Yield colorless products on decomposing: and (4)
formaldehyde or equivalent substance under al- 25
it should not give oil! an acid so strong or so re- kalinc.- neutral. or acid conditions. and Obtain
active that it might react with the steel oi the thereby a hvdroph?lc. or even water-soluble. son
die and thus bring about corrosionl It is the
densation product. This ‘may be incorporated
Purpose and object or the prevent invention to
with a cellulosic material such as. for ample.
30 provide molding compositions with a compound
of this character which will operate to materially
facilitate-the hot pressing of urea-aldehyde compositions in the formation of light-colored shaped
articles of ample water, shock and heat resist-
paper'pulp. alpha cellulose. wood ?our. and the so
like. In so doing, the urea-formaldehyde resin
reacts with the ‘cellulose to produce what is
known as 8- Elllcwure “impound- Ill is neces
sary to remove from the mixture the solvent.
_ 35 ance.
I have discovered that the prerequisites of a
usually water, in which the urea-formaldehyde 35
condensation was accomplished. This can be
latent catalyst are possessed by the salts of the
mono- and dl-halogenated aliphatic‘ carboxylic
acids and by the salts of halogenated acetic acid
40 and alpha and alpha-beta halogenated 110m‘)-
done by drying, either at atmospheric or reduced
pressure, at atemperature desirably below 00° C.
The dried material is usually ?nely mum! and
screened. It is customary to include a curing 4o
loglles of acetic acid in‘particular. Rather pe-_ citslyst 1mg!taiiulza??céssufh as zinc stesrste- ‘
"marl? the twins property possessed by the
a “me 1"’
mono- and (ii-halogen compounds is not evinced
A convenient way to incorporate the catalyst
is simply to dissolve the salt in the resin syrup
4' by the m'halogen °°mp°“nds' As 8mm‘ ex‘
" amples of such compounds may-be menubned
bef
‘
' the latter'is mixed with the drier
Wet- 4s
ti ore’ents such as ethyl alcohol or acetone may
salts such as chloracetates bromacetates iodoa t t
'
’
.
“8 “g
'
,
be added if desired.
ce a es. iiucracetates, dichloracetates, a-chlorpmpmmm- “*‘dlchmrpmpmm?f “'P'dibmm‘.
ougmy grind the dried glucamue mixture with
the dry salt. I: this method is used. the catalyst '
5° pmpl‘mates' “'p‘dlcmrsteames and the ' ukeI The salts may be of any base metal but, 91110118
.those preferred may be mentioned sodium, ‘10tassium, ammonium, aluminum, zinc, calcium,
magnesium, and so forth; Such metals as lead
55 and mercury are applicable but are ‘not desirable
Another way is to thor- .
should be groundin before the lubricant is added. so
for after such a substance as zinc stearate is
added’ grinding is practically impossible‘
Having a molding compound containing’ reac
tive urea-formaldehyde resin (combined it de-u
sired ‘as a glucanure compound with the filler). l5
2
.
2,138,689
_.
The product was molded at 140° 0., 3500
pounds
per square inch, for 5 minutes. The
vention, and a lubricant, the composition may be '
subjected to hot pressing usually e?’ected at a moldings obtained were well‘ cured, possessed a
high glaze, were light colored and translucent.
temperature of about 125 to 150° C. under a pres
Example 4.-—A blank molding composition was
sure of from about 2000 to 3500 pounds per square
prepared
as follows: 1000 parts of neutral 37%
inch, to mold any desired article. The salts of aqueous formaldehyde
and 500 parts of urea were
the halogenated acids liberate an acid substance boiled under re?ux for
1 hour. The resulting
under molding conditions, and eiiectively harden
the resin. It should be noted that the catalysts syrup was mixed with 400 parts of alpha ?ock, 10
at 64° C. and ground.
claimed do not liberate dangerous hydro-halogen dried
The powder was activated with 1 per cent zinc
acids, but merely the comparatively innocuous
carboxylic acid which is suiiicient, however, to monochloracetate by grinding the powder and
a latent curing catalyst as provided in this in
bring about a cure.
This is important because
repeated use of molding compositions containing
15 curing catalysts which depend on the liberation
of, say, hydrogen chloride or bromide, as the ac
tive principle tends to cause pitting, staining and
corrosion of molds, thus deteriorating an expen
sive piece of apparatus. Furthermore, these cat
alyzing salts are comparatively cheap, easy to
prepare, substantially stable at ordinary temper
atures, are light colored themselves and yield
light-colored products, have relatively low molec
ular weights, and are hence e?lcient and eco
nomical.
dry salt in a ball mill; 0.25 per cent zinc stearate
was also ground in. The product was molded
at 140” C., 3500 pounds per square inch, for 5 15
minutes.
The molded objects were quite translucent,
light colored, well formed and glazed.
The ?ow ‘
of the composition was soft. A molding, im
mersed in boiling water for 15 minutes, absorbed 20
4.5 per cent moisture, which is average for a
urea-formaldehye molding composition.
Example 5.--Uslng a blank molding composi
tion prepared as described in the first paragraph
of Example 4, it was activated by grinding in a 25
ball
mill with l per cent of ammonium mono
In presenting the following examples illustra
tive of the invention, I do not wish to be limited -chloracetate. The moldings made at 140° C.,
3500 pounds per square inch, for 5 minutes, were
by their procedures or proportions, as modifica
substantially of the same appearance as those
tions within the scope of the invention will pre
of Example 4, the composition curing satisfac 80
sent themselves to one skilled in the art.
Example 1.—1120 parts by weight of a 37%
formaldehyde solution and 552 parts by weight
urea were boiled under re?ux at pH '7 for 1 1/2 hours.
0f the resulting syrup, 200 parts were mixed with
62 parts of alpha flock and the composition was
dried at 64“ C. in a‘current of air, and ground.
This material was hot-pressed at 140° C., for 5
minutes, without, adding any activator. It would
not cure, the moldings being soft and sticky, of
wan heterogeneous appearance, and possessing
low mechanical strength.
100 parts of the powder and 1 part of the so
dium salt of monochloracetic acid were ground
together in a ball mill and subsequently further
'
.45 ground with 0.35 part of zinc stearate.
The activated composition was molded at 140°
C., 3500 pounds per square inch, for 5 minutes.
-The material was soft ?owing, the moldings
being well formed and glazed, white strong, and
translucent. An object was immersed in boil
ing water for 15 minutes and it was substantially
una?ected, the glaze remaining excellent.
A portion of the composition was stored in a
torily.
Example 6.-Example 5 was repeated using 1
per cent of calium monochloracetate. Excellent,
well cured, translucent, light-colored objects were
formed on molding. After being immersed in, 35
boiling water for 15 minutes, the moldings ab
sorbed an average of 2.1 per cent water.
Example 7.--Example 5 was repeated using 1
per cent sodium ¢-chloropropionate. The flow of
the finished composition was soft. The molded
articles were well formed, cured, and glazed, light
colored, and translucent. when immersed in
boiling water for 15 minutes the molded pieces
absorbed 3 per cent water.
Example 8.—Example 5 was repeated using 1 45
per cent ammonium a-chloropropionate as the
activator. The appearance of the molded prod
ucts was the same as of those produced according
to Example 7.
.
Example 9.——Sodium iodoacetate was tested fol
50
lowing the procedure of Example 5. The mold
ings were light colored, very translucent, well
formed and glazed, strong and apparently well
cured. The flow of the composition was soft.
Example 10.—Example 9 was repeated, using
as before. Again the flow was soft and molded
objects were obtained which were .well cured. sodium bromo-acetate.‘ The moldings obtained
The powder did not deteriorate in storage.
, ~ were well cured, and resembled those of Example
Example 2.—A blank molding composition was 9 in appearance. when immersed-in boiling wa
prepared as described in the ?rst paragraph of ter for 15 minutes, the glaze was scarcely affected
Example 1. This was activated with 1 per cent and the water absorption was 7.4 per cent.
What I claim is:
sodium dichioracetate by grinding the compo
1. A urea-formaldehyde molding composition
nents together in a, ball mill. Zinc stearate was
containing a latent catalyst comprising a salt of
also added to the extent of 0.25 per cent.
The ?nished composition was molded at 140° chloracetic acid.
2. A urea-formaldehyde molding composition 05
0., 3500 pounds per square inch, for 5 minutes.
‘ vThe molded objects were well formed and glazed, containing a latent catalyst comprising a salt of
closed container for 71/2 months, and then molded
light colored and translucent.
Example 3.-l50 parts of 37% formaldehyde
chlorpropionic acid.
3. A urea-formaldehyde molding composition
solution and '75 parts of urea were boiled together
under re?ux at pH 7 for 1 hour. ‘1.5 parts of
containing a latent catalyst comprising a salt of
neutral sodium-monochloracetate were added to
from the class consisting of the mono- and di
the syrup and the whole mixed with 60 parts of
alpha ?ock. The mixture was dried in a current
of air at 60° C. and subsequently ground to a
76 powder.
a halogenated aliphatic‘ carbomlic acid selected " 3
halogenated straight chain mono-carboxylic acids
which remains substantially neutral before being
broken down by heat and pressure during molding
and which, upon being broken down, liberates an
Cl
3
8,188,689
acid not corrosive to the metal structure of molds.
4. In the process of making a urea-formalde
hyde molding composition. the step 0! adding a
latent catalyst comprising a salt 01’ .chloracetic
acid, to a mixture comprising cellulose and urea
ionnaldehyde resin.
5. In the process oi’ making a urea-formalde
hyde molding composition, the step of adding a
latent, catalyst comprising a salt of chlorpropion
ic acid to a mixture comprising cellulose and
10 urea-formaldehyde resin.
6. In. the process 01’ making a urea-formalde
‘ hyde molding composition, the step of adding to
a mixture comprising cellulose and urea-formal
dehyde resin. a latent catalyst comprising a salt
15 or a halogenated aliphatic carboxylic acid select
ed from the class consisting 'of the mono- and‘
di-halogenated straight chain mono-carboxylic
acids which remains substantially neutral beiore
being broken down by heat and pressure during
molding and which, upon being broken down. lib
erates an acid not corrosive to the metal structure
of molds.
canure and a small proportion of a salt of chlora
cetic acid.
8. A molding composition comprising a glu- _
more and a small proportion of a salt of a
chlorinated straight chain mono-carboxylic acid
selected from the class consisting of the mono
and di-halogenated straight chain mono-car
boxylie acids which remains substantially neutral
bei'ore being broken down by heat and pressure
during molding and which is reactive at molding l0
temperature to release a curing proportion 01 an
acid not corrosive to the‘ metal structure of molds.
9. A molding composition comprising a glu
canure and a small proportion of a salt of a
halogenated aliphatic carboxylic acid selected
from the class consisting of the mono- and di
halogenated straight chain
mono-carboxylic
acids which remains substantially neutral before
being broken down by heat and pressure during
molding and which is reactive at molding tem
perature to release a curing proportion of an
acid not corrosive to the metal structure oi molds.
‘
'l. a molding composition comprising a sin
CARLETON ELLIS.
DISCLAIMER
Unna Amman Momma Comosrnons
2,133,689.—0arleton Ellis, Montclair, N. .i.Camus-r.
Patent dated October 18, 1938.
CONTAINING a LATENT Cosmo
Disclaimer ?led July 22, 1941, by the assignee,Plaskoa 0ompwny,y1morpo
rated.
,
7 of said patent; and further disclaims from claim
Hereby disclaims claims 1 and compositions
containin a latent catalyst in wlnch
'3 all urea-formaldehyde mold'
er disclaims from claim 8
said latent catalyst is a salt of c
loracetic acid; and furt?
'
ortion of a salt
all moldin compositions comprising a glucanure andasmallpro
saltisasaltof
xylic
acid
in
which
sai
_ _
of a chlorinated stra' ht chain monocarbo
further
disclaims
from
claim
9
all
molding
cczgipositions
chloracetic acid‘; and
phaticcom
car
rising a glucanure ‘and a small proportion of a salt of a halogens
xylic acid in which said salt is a salt of chloracetic acid.
ah
3
8,188,689
acid not corrosive to the metal structure of molds.
4. In the process of making a urea-formalde
hyde molding composition. the step 0! adding a
latent catalyst comprising a salt 01’ .chloracetic
acid, to a mixture comprising cellulose and urea
ionnaldehyde resin.
5. In the process oi’ making a urea-formalde
hyde molding composition, the step of adding a
latent, catalyst comprising a salt of chlorpropion
ic acid to a mixture comprising cellulose and
10 urea-formaldehyde resin.
6. In. the process 01’ making a urea-formalde
‘ hyde molding composition, the step of adding to
a mixture comprising cellulose and urea-formal
dehyde resin. a latent catalyst comprising a salt
15 or a halogenated aliphatic carboxylic acid select
ed from the class consisting 'of the mono- and‘
di-halogenated straight chain mono-carboxylic
acids which remains substantially neutral beiore
being broken down by heat and pressure during
molding and which, upon being broken down. lib
erates an acid not corrosive to the metal structure
of molds.
canure and a small proportion of a salt of chlora
cetic acid.
8. A molding composition comprising a glu- _
more and a small proportion of a salt of a
chlorinated straight chain mono-carboxylic acid
selected from the class consisting of the mono
and di-halogenated straight chain mono-car
boxylie acids which remains substantially neutral
bei'ore being broken down by heat and pressure
during molding and which is reactive at molding l0
temperature to release a curing proportion 01 an
acid not corrosive to the‘ metal structure of molds.
9. A molding composition comprising a glu
canure and a small proportion of a salt of a
halogenated aliphatic carboxylic acid selected
from the class consisting of the mono- and di
halogenated straight chain
mono-carboxylic
acids which remains substantially neutral before
being broken down by heat and pressure during
molding and which is reactive at molding tem
perature to release a curing proportion of an
acid not corrosive to the metal structure oi molds.
‘
'l. a molding composition comprising a sin
CARLETON ELLIS.
DISCLAIMER
Unna Amman Momma Comosrnons
2,133,689.—0arleton Ellis, Montclair, N. .i.Camus-r.
Patent dated October 18, 1938.
CONTAINING a LATENT Cosmo
Disclaimer ?led July 22, 1941, by the assignee,Plaskoa 0ompwny,y1morpo
rated.
,
7 of said patent; and further disclaims from claim
Hereby disclaims claims 1 and compositions
containin a latent catalyst in wlnch
'3 all urea-formaldehyde mold'
er disclaims from claim 8
said latent catalyst is a salt of c
loracetic acid; and furt?
'
ortion of a salt
all moldin compositions comprising a glucanure andasmallpro
saltisasaltof
xylic
acid
in
which
sai
_ _
of a chlorinated stra' ht chain monocarbo
further
disclaims
from
claim
9
all
molding
cczgipositions
chloracetic acid‘; and
phaticcom
car
rising a glucanure ‘and a small proportion of a salt of a halogens
xylic acid in which said salt is a salt of chloracetic acid.
ah
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