close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2406339

код для вставки
Patented Aug. 27, 1946
2,406,339
/
UNITED
STATES
PATENT ‘OFFICE ._ " r
‘ 2,406,359
PRODUCTION or assmocs MATERIALS
Darwin E. Badertscher and Henry G. Berger,
Woodbury, and Richard B. Bishop, Pitman,
N. J., assignors to Socony-Vacuum Oil Com
pany, Incorporated, a corporation of New York
No Drawing.
Application October 30, 1942,
Serial No. 463,894
7 Claims.
(Cl. 260-51)
1
This invention has to do with the production
of phenol-formaldehyde type resins.
Resins of the phenol-aldehyde type, that is.
those obtained by the condensation of a phenol
and an aldehyde, are ‘Well known to those fa
miliar with the art. Numerous procedures have
been proposed for the preparation of these resins;
in general, catalytic procedures have been more
2.
ated hydroaromatic hydrocarbon may be em
ployed.
The process contemplated herein for the pro
duction of phenol-formaldehyde resins involves
the following: Phenol and formaldehyde, for ex
ample, are allowed to react in the presence of hy
drogen ?uoride which may be anhydrous or in
aqueous solution. Formaldehyde may be used in
the gaseous phase, aqueous solution or solid phase.
bases and salts have all been credited with the 10 The amount of hydrogen fluoride used may be
ability to facilitate the condensation of phenol
varied considerably; however, about 5 per cent
and formaldehyde and thereby produce resins of
to about 20 percent by weight of the reactants
different degrees of solubility in acids, bases and
is preferred. The reaction or condensation may
solvents, color, toughness, stability, etc. Unless
be carried out at low temperatures, such as, for
great care is exercised in their preparation, the 15 example, room temperature (20—25° C.) or below,
successful than the non-catalytic. Various acids‘,
resins of this type tend to bedark in color and
relatively unstable to the action of light and air.
or at elevated temperatures.
At low tempera
tures, such as 20-25° C., however, the reaction is
The decolorization of a dark resin of this type, or
Very slow, particularly when aqueous hydrogen
the precautions necessary for the preparation of
?uoride is used as the condensing agent. rAlso,
a light-colored resin, appreciably increases the 20 the hydroxylated aromatic or hydroxylated hy
cost of the resin.
droaromatic compounds used are often solid at -
This invention is predicated upon the discov
such temperatures and inef?cient mixing of the
ery-that the condensation of phenol with form
reactants may result. A preferred temperature
aldehyde, and more broadly the condensation of
range is from about 80° C. to about 120° C. It is
a hydroxylated aromatic or hydroxylated hydro 25
bene?cial
to stir the reaction mixture during the
aromatic hydrocarbon with an aldehyde, is aided
course of the reaction or condensation. Nat
by hydrogen ?uoride. The resins obtained by
urally, in view of‘ the action of hydrogen ?uoride
such condensation arelight-colored, and. as such
on glass, it is desirable to use a metallic reaction
are more desirable than those obtained with other
vessel such as one of copper, stainless steel or iron.
acidic condensation agents.
>
30 The reaction product is washed with large quan
The condensation contemplated herein is
titles of water to remove hydrogen ?uoride and
adapted for resini?cation of hydroxylated aro
any Water-soluble products formed in the reac
matic or hydroxylated hydroaromatic compounds
tion. The water-insoluble resinous reaction prod »
with all aliphatic and aromatic aldehydes, typical
ucts are separated from the water washings and
of which are formaldehyde, acetaldehyde, butyr-v
aldehyde, benzaldehyde, etc, in the presence of
Althoughthe proportions of the reactants, al
HF. Preference is given to the aliphatic alde
dehyde and hydroxylated aromatic or hydroxyl
hyde's and particularly preferred herein is form
ated hydroaromatic hydrocarbon, may be varied
aldehyde.‘
_
considerably in order to obtain resins with vary—
As aforesaid, hydroxylated aromatic 0r hy 40 ing
properties, it is preferred that a slightly
droxylated hydroaromatic hydrocarbons con
larger molar quantity of aldehyde than said hy
dense with the foregoing aldehydes in the pres
droxylated aromatic or hydroxylated hydroaro
ence of hydrogen ?uoride. Mono- and poly- hymatic hydrocarbon be used. For example, to ob
droxylated, mono- and poly- cyclic aromatic hy
drocarbons are contemplated herein and repre 45 tain a truly infusible phenol-formaldehyde resin,
a ratio of about 7 mols of formaldehyde to about
sentative of which are the following: phenol,
6 mols of phenol is preferred.
dried.
'
_
.
cresols, p-tertiary butyl phenol, p-tertiary amyl
The following examples serve to illustrate the
phenol, resorcinol, alpha- and beta- naphthols,
new process and the resins obtained thereby.
mono- and poly- hydroxy methyl naphthalenes,
mono- and poly- hydroxy polymethyl naphtha 50
Example I
lenes, etc. Phenol, cresol, p-tertiary butyl‘ phenol
_A mixture of 160 grams of phenol, 160 grams
and p-tertiary amylphenol are particularly pre
of 37% aqueous formaldehyde solution and 50
ferred hydroxylated aromatic hydrocarbons for
the purposes‘ of this invention.
In place of a
hydroxylated aromatic hydrocarbon, a hydroxyl
cc. of 48% hydro?uoric acid was stirred in an
open copper vessel for ten minutes. No visible
55 evidence of reaction was observed. The copper
’ 2,406,339 -
4
3
formaldehyde and said phenol in the presence
of hydrogen ?uoride whereby the reaction time
is substantially decreased as compared with other
acid condensation catalysts, without substantial
darkening of the product.
vessel was then placed on a hot~plate and the
contents heated, with agitation, to about 100° C.
for about ?fteen minutes. The mixture foamed
considerably and an insoluble gummy material
separated. The beaker'was then removed from
the hot-‘plate, the contents were'stirred for‘?ve
7 3-..In .a process for the production of a resin
ous product by the condensation, in the presence
minutes more and: the reaction mixture. was .then
of an acid condensing agent, of formaldehyde and
drowned vin cold water. A water-insoluble resin
phenol, the improvement affording a substan
ous material was separated from the water »
tially reduced reaction time and a light colored
10
phase and repeatedly leached withv water, It
product which comprises condensing said form
was then dried thoroughly. One hundred and
aldehyde and said phenol in the presence of
ninety‘ grams of a hard, infusible, light-ivory col
from about 5 per cent‘ to about 20 per cent by
ored resin was thus obtained.
‘
Example I1
‘
'
V '. weight of hydrogen?uoride based on the weight
n
15 "of the reactants whereby the reaction time is
V
substantially decreased as compared with other
A mixture of 92 grams of phenol, 80 cc. of
‘ .acid condensation catalysts, without substantial
37% aqueous formaldehyde and 4 cc. of 48% hy- '
darkening of the product.
dro?uoric acid was‘ stirred and heated to about
100° C. in a copper beaker on a hot-plate.’ The
4. ‘In a process for the production of a resin
reaction mixture became’jtaffy-like in consistency
after drowning in water. The insoluble, viscous
material waspwashed well with'water. The .ma
ous product by the condensation, in the pres-'
ence of an acid condensing agent, of formalde
terial remained soft, was pink in color and did'not
harden when spread and worked on a hot-plate
colored product which comprises condensing said
hyde and phenoLthe improvement affording a. '
substantially reduced reaction time and a light
25
with a spatula. .
formaldehyde and said phenol at a temperature
of from about 80° C. to about 120° C‘. in the
Example jIII '
presence of from about 5 per cent to about 20
per cent by weight ofv hydrogen ?uoride based
A mixture of 164 grams of p-tertiary amyl phe
on the weight of the reactants whereby the Ice
nol, 80 grams of 37% aqueous formaldehyde and
grams of 48% hydro?uoric acid was stirred 30 action time is substantially decreased as com;
pared with other acid condensation catalysts.
and boiled in an open copper beaker at about
without substantial darkening of the product, .
110° C. for thirty minutes. After washing'and
5. In a process for the production of a resin
drying, as described above in Example I, 160
ous product by the condensation, invthe pres
grams of an off-white solid resin, which hardened
ence of an acid condensing agent, of formalde
wh'en'melted, spread and worked with _a spatula
on a 150° C. hot-plate, were obtained.
'
hyde and‘ phenol, the improvement affording a
substantially reduced reaction'timeand a light
colored product which comprises condensingsaid
formaldehyde and said phenol in the molar ratio
‘
Example IV
VA mixture of 150 grams of p-tertiary 'butyl
phenol, 95 grams of 37% ‘formaldehyde and 35
grams of 48% aqueous hydro?uoric acid was
40, of about 7:6 at ‘a temperature‘of from about
80° C. to about 120° C. in the presence of hydro-_
gen ?uoride whereby the reaction time is. sub
stantially decreased as compared with other acid
condensation catalysts without substantial darka,
ening of the product.
stirred and heated at about 110° C. for 45 min‘
utes. By working up and washing, as described
above in Example I, 149 grams of‘ a light-‘amber
solid resin, which hardened when melted, spread
6,. In a process for the production of a resin
ous product by the condensation, in the presence 7
and, worked with a spatula on a ‘150° 0. hot
plate', were obtained.
'
7'
_
of an acid condensing agent, of formaldehyde
It is to be understood that the foregoing ex
and tertiary butyl phenol, the improvement af
amples are illustrative only and that the inven
tion is not limited thereto, rather the invention 50 fording a substantially reduced reaction time and
a light colored (product which comprises ‘con
is to be construed broadly as coming within the
densing said formaldehyde and said tertiary bu
scope of the appended claims.
.
tyl ‘phenol in the presence of hydrogen ?uoride
whereby‘ the reaction time is substantially de
1. In a process for the production of a'resin
creased as compared with other acid ‘condensa
ous product by the condensation, in the'presence
tion catalysts, without substantial darkening of
of an acid condensing agent, of formaldehyde
We
claim:
7
,
‘
.
-
and a material selected from the group consist
the product.
‘
-
I
v
7. In avprocess for they production of a resin
ous product by thecondensation, in the presence
ment affording a substantiallyv reduced reaction
time and a light colored product which com 60 of an acid condensing agent, vof formaldehyde‘
and tertiary amyl'phenol, the improvement af
prises condensing said formaldehyde and said
ing of phenols and'cyclohexanol, the improve
fording a substantiallyv reduced reaction time
material in the presence of hydrogen fluoride
and a light colored product which comprises con
whereby the reaction time is substantially de
densing said formaldehyde and said tertiary
creased as compared with other acid condensa
tion catalysts without substantial darkening of 65 amyl phenol in the presence of hydrogen ?uoride
whereby the reaction. time is substantially dethe product.
creased ascompared with other acid condensa
2. In a process for the production of a resin
tion catalysts, without substantial darkening of
ous product by the condensation, in the presence
of an acid condensing agent, of ‘formaldehyde
and a phenol, the improvement affording a sub- '
stantially reduced reaction time and a light col
' ored product which comprises condensing said
the product. .
70
’
DARWIN lE. BADERTSC-Iv-IER.
HENRY G. BERGER.
RICHARD .B. BISHOP.v
_
~
Документ
Категория
Без категории
Просмотров
0
Размер файла
348 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа