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Патент USA US2128879

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mama Aug. so, 193s
. 2,128,879
Kenneth M. irey and Lawrence M. Debing, Pali
sadel Park, N. 1., asslgnors to Resinox Corpo
ration, New York, N. Y., a corporation of Dela
No Drawing. Appllcation November 14, 1936,
Serial No. 49.138 ‘
'1 Claims. (01. 106-2!)
Our invention relates to the production of res
inous impregnating materials. More speci?cally,
our invention relates to the production of an im
proved impregnating material having a resinous
5 base formed by the condensation of aldehydes
with bis- [hydroxy aryl] di-alkyl methanes and/or
their ketone condensation produc
Numerous impregnating agents having phe
nolic resin bases have been recommendedin the
10 past but these have in most cases been prepared
by the reaction of aldehydes with free phenols or
materials containing free phenols. Such prod
ucts are, therefore, disadvantageous for many
Purposes, especially for impregnating objects‘
15 which come in contact with foodstu?s.
One object of our invention, therefore. is the '
preparation of a resinous impregnating material
having as a base a condensation product of sub
stances containing no free phenols. A further ob
m ject of our invention is the preparation of an im
pregnating material which, upon application and
heat treatment. will have satisfactory bonding
properties, ?exibility,
toughness, and water re
sistance. Further objects and advantages of our
invention will be apparent from the following
The impregnating agents of our invention com
ample below with reference to the preferred ma- -
terial, i. e.. a mixture of beta.beta-bis- [4-hy
droxy-phenyll-propane and beta.beta-bis- [4-hy
droxy - phenyll-propane-acetone condensation
Beta.beta-bis- [4-hydroxy-phenyll-propane is a
white crystalline material with a melting point
of 150 to 154°‘ C. This material may be prepared
by any of the known methods, as for example, by
the method described by W. A. Beatty in U. S. 10
Patent No. 1,225,748, granted March 15, 1917.
Betabeta-bis- [4 - hydroxy - pheny1l-propane-
acetone condensation product may be prepared by
reacting approximately equal molecular propor
tions of acetone and the crystalline product de- 15
scribed above, in the presence ‘of an acid catalyst
such as hydrochloric acid, at'temperatu'res of '70
to 80° C. This material may also be prepared by
. any other suitable procedure as, for example, that
disclosed in co-pending application U. 8. Serial 20
No. 680,230 referred to above. The beta.beta-bis
[4-hydroxy-phenyll-propane-—acetone conden
sation product prepared by any‘of these proce
dures is a reddish colored resinous material hav
ing a melting point around 50° C.
* '-
The mixed intermediate which we' prefer to
utilize in the present process cpnstitutes a mix
ture of approximately equal proportions of the
prise ‘suspensions, in relatively non-volatile sol
beta.beta-bis- [4-hydroxy -'phenyll-propane and
vents, or plasticizers,
the beta.beta-bis-[4-hydroxy-phenyll-propane- 30
” tion products of aldehydes with bis- [hydroxy ' acetone condensation product. This intermediate
aryll-di-alkyl methanes, or mixtures of such sub
may be prepared by simply mixing the materials
stituted methanes with their ketone condensation prepared as above described, or, as has been pre-'
products. We’prefer to: employ such a mixture, viously pointed out, this intermediate may be .
as for example, a mixture of beta.beta-bis-[4
formed- in a single reaction from‘the correspond- .35
hydroxy-phenyll-propane and beta.beta-bis-[4
hydroxy-aryl compound and hetone. The
hydroxy-phenyll -propane-'-acetone condensation ing
proportions of the two ingredients of the mixed
product. _Mixed reaction products of this type intermediate may be varied within rather wide
of hydroxy
may be formedby the interaction
aryl compounds and ketones. Bis- [hydroxy
aryll-di-alkyl methane constitutes the primary
crystalline reaction product of 2 mols of the
corresponding hydroxy-éaryl compound with _1
mol. of a ketone. Bis- [hydroxy-aryl] -di-alkyl
methane-ketone condensation product repre
sents the further reaction ‘of the primary crys-_
_ talline product with additional ketone.
products may be
quently mixed as described below, or a mixture of
the materials may suitably be‘prepared in a single
50 reaction from the. corresponding .hydroxy-aryl
compounds and ketones, in accordance with the
‘ process described in co-pending application Serial
' No. 680,230 by K. M. Irey and L. C. Swallen. The
of preparing the compounds separately
‘5 and subsequently mixing is described in the ex
limits and, in fact, either one of the materials
may beused separately. However. in general we 40
prefer to utilize a mixture of approximately the
proportions described above.
The second step of the process for preparing
our improved impregnating materials constitutes
the reaction of the mixedintermediate product 45
described above with an aldehyde such as form
aldehyde or one of its polymers. This reaction
islcarried to a definite stage as indicated by
the “dry rubber". test, after which the product
is immediately mixed with a high boiling solvent, 50 _
or plasticizer, to yield the ?nal impregnating ma
terial. The "dry rubber" test utilized in this
connection measures the degree of heat reactivity
of the resinous product in terms of the time
required to eliminate tackiness in a sample placed 55
on a hot plate maintained at 150° C. The re
sults of this test, as given in the example be
low, refer to time in seconds for a sample of the
product to lose its tacklness on the hot plate.
The aldehyde reaction proceeds at an ex
tremely slow rate in the absence of a catalyst
and we therefore prefer to utilize an ‘alkaline
The impregnating agents prepared as above
described may be employed for any of the pur
poses for which previously known materials of
this general type have been used, e. 3., as ad
hesives, coating materials, etc. The usual meth
ods of application may be employed and the usual
methods" of heating may- be used to transform
the impregnating material to the insoluble stage.
employed as ‘condensation catalysts, give rise For example, various fibrous materials may be
to a marked acceleration of ‘the ‘reaction but coated with the impregnating agent by dipping,
brushing, spraying and the like, and may subse
nevertheless require a considerable period of
time to carry the reaction’to the preferred stage quently be baked in an oven until the resinous
condensation catalyst for this reaction.
10 terials such as barium hydroxide, which are often
coating or bond reaches the desired stage of
for the present process. We have found that lime
15 exerts a more pronounced accelerating e?ect
and that a mixture of lime and barium hydroxide
insolubility and toughness. Various other uses,
such as the application of an “enamel" coating
constitutes an eminently satisfactory catalyst for ' to wire, will also be'apparent to those skilled in
this purpose.
Utilizing a'catalyst comprising‘
four parts of barium hydroxide and one part
of lime, this reaction may generally be carried
to the desired stage in a period of about 30
minutes. Although we prefer to employ a mix
ture of this nature, it may be said that any
alkaline earth catalyst will be operative in our
25 process.
The condensation reaction may be illustrated
by the ‘following speci?c example: 100' parts
of the mixed intermediate product described
above are placed in a resin kettle, melted and
then cooled to approximately 60° C. The mass
is then thoroughly’ mixed vwith '70 parts of a
40% formaldehyde solution after which 4 parts
of barium hydroxide and one part of lime are
added in the form of-an aqueous suspension. The
35 ‘resulting mixture is then reacted under heat
until a sample exhibits a dry rubber test of
approximately 15 to 25 seconds. When this
‘point is reached, the application of heat is im
mediately stopped and the plasticizer, e. g., di
40 ethylene glycol, is added as quickly as possible.
The amount to be added will depend upon the
the art.
The desirable properties of our im
pre'gnating material will best be taken advantage
01', however, in the impregnation of materials
which comein contact with foodstuffs. In such
uses the desirable properties of our impregnating
agents, such as water impermeability and free
dom from taste and odor
are highly advanta
It is to be understood, of course, that our 25
invention is not to be limited to the particular
examples given above by way of illustration.
Equivalent reactants and varying proportions or
reaction conditions may be employed depending
upon the exact nature of the product desired. 30
For example, instead of employing beta.beta-bis
[4-hydroxy-phenyl]-propane and its acetone
condensation product, any of the homologues of
these materials could be employed, Also, in place
of formaldehyde, its polymers such as paraform 35
aldehyde or hexamethylene-tetramine, or its
homologues such as acetaldehyde could be uti
lized. Likewise, any suitable high boiling solvent
orpla'sticizer', such as glycerine, which is com
patible with the resinous reaction product and
desired plasticity of the impregnating material, ' the‘water contained in such product, and which 40
but for most purposes should be just su?icient is chemically inactive at the temperatures em
to‘ bring the material to the state of a thin liquid ' ployed, could suitably be substituted for the di
45 having a dry rubber test of approximately '40 , ethylene glycol specified in the example. In
The dry rubber, value of the material maybe
varied within rather wide limits, e. g.. 15 sec.
to 90 sec., depending on the desired degree of
60 heat reactivity of the product. For some pur
poses /it is preferred
to carry the reaction at '
this stage as far as possible without transform
ing the product to the insoluble or rubbery stage.
The dry rubber test of 15 to 25 seconds repre
65 sents a safe practical limit, but the reaction may,
of course, be carried further if precautions are
taken to cool the material by adding the plas-'
ticizer before the insoluble stage is reached.
The plasticizer apparently acts only‘in a physi
general it may be stated that any equivalents
or modi?cations of procedure which would natu 45
rally‘occur to one skilled in the art are included
within the scope of our invention.
' Our invention now having been described what
we claim is:
1. Ina process for the production of a resinous 50
material by heat reacting a mixture ofv a bis
[hydroxy-aryll-di-alkyl methane and a bis
[hydroxy-aryll-di-alkyl methanHetone con
densation product with a‘ su?lcient proportion
of an aldehyde to form an insoluble infusible
product when fully reacted, the improvement
which comprises carrying ‘the reaction to an
60 cal manner as a solvent or plasticizing agent and
advanced stage evidenced by a dry rubber test
does not enter into reaction with the resinous 4 of 15 tol25 seconds, ,and then immediately pre- .
venting substantial further reaction by ceasing
mass. The increased time value of the dry rub
ber test, after addition of the plasticizing agent ‘ the application of heat and introducing a plas
the condensation product
‘does not indicate a change in the nature of the ticizer compatible with
65 resin but merely a physical e?'ect of- the presence thus produced.
2. ‘In a process for the production of a resinous
of the plasticizer. It will be apparent, there
fore, that any other organic solvent-or placticizer material by heat reacting a mixture of beta.
beta-bise[4-hydroxy-phenyll-propane and beta‘.
for the particular resin produced may be suc
- cessfully employed‘.
beta-b'is- [qt-hydroxy-phenyl] v-propane — acetone
Any such material, how
condensation product with a sufficient proportion
70 ever, should preferably be su?'lciently non-vola
of formaldehyde to form an ‘insoluble infusible
tile to exerta plasticizing e?'ect in the ?nal mass
product when fully. reacted, the‘ improvement 70
""of impregnating material after application and which
comprises carrying the reaction to an ad
heating, and should, of course, be chemically
inactive towards the resinous mass and the ma
75 terlals to be impregnated.
vanced stage evidenced by a dry rubber test of
15 to 25 seconds, and then immediately prevent
ing substantial further reaction by ceasing the 76
application of heat and introducing a plasticizer
compatible with the condensation product thus
3. In a process for the production of a resinous
material by heat reacting a mixture of beta.beta
bis-l4-hydroxy-phenyll-propane and beta.beta
‘ bis-[*i-hydroxy-phenyl]-propane-acetone
densation product with a su?‘icient proportion
of formaldehyde to form an insoluble infusible
product when fully reacted, the improvements
which comprise effecting the reaction in the
presence of an alkaline earth catalyst contain
ing lime, carrying the reaction to an advanced
stage evidenced by a dry rubber test of 15 to
25 seconds, and then immediately preventing
substantial further reaction by ceasing the ap
plication of heat and introducing a plasticizer
compatible with the condensation product thus
4. In a process for the production of a‘ resin
ous material by heat reacting a mixture of beta.
beta-bis- [4-hydroxy-phenyll-propane and beta.
beta-bis- [4 -hydroxy-phenyl] -propane — acetone
condensation product with a su?icient propor
tion of formaldehyde to form an insoluble in
fusible product when fully reacted, the-improve
ments which comprise effecting the reaction in
the presence of a catalyst consisting of four
parts of barium hydroxide and one part of lime,’
carrying the reaction to an advanced stage evi
denced by a dry rubber test of 15 to 25 seconds,
and then immediately preventing substantial 10
further reaction by ‘ceasing the application of
heat' and introducing diethylene glycol into the
condensation product thus produced in an
amount su?icient to increase the dry rubber test
of the ?nal product to approximately 40 seconds. 15
5. The product of the process of claim 1.
_ 6. The product of the process of claim 2.
7. The product of the process of claim 2 char
acterized by a degree of reactivity evidenced by
a dry rubber test of approximately 40 seconds. 20
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