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Патент USA US2409278

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Patented Oct. 15, 1946
, 2,409,276
UNITED’ STATES PATENT OFFICE
2,409,276
COMPOSITIONS COMPRISING BLOWN TER
PEN'IC PRODUCTS AND VINYL POLYMERS
AND METHOD OF MAKING
'
Mortimer T. Harvey, East Orange, N. J.,' assign- ’
on; to Harvel Research Corporation, a comra
tion of New vJersey
.' Application August 1, 1041,
No Dra
Serial No. 405,078
11 Claims. (01. zoo-as)
1
The present invention relates to compositions
of matter which comprise blown terpenic prod
ucts and vinyl polymers in which compositions
the present invention is particularly concerned
with the various terpenes by which term, are
meant unsaturated, non-aromatic hydrocarbons
the oxidized terpenes serve as a plasticising sol
'oi' the formula (CsHa)n. where n is an integer
vent for the vinyl polymers.
greater than 1, as well asressential oils consisting
largely of such hydrocarbons. To cover such es
sential oils, as for ‘example, cedar wood oil, as
-
The compositions of the present invention can
be used as such, for example, as ?lms, coatings,
paints and varnishes for electrical insulation, for
well as the individual terpenes, the all-embracing
protective coatings, for decorative coatings and _ term "terpene oils” will be used.
The method of oxidation particularly de
so on where they are applied with a volatile thin 10
ner or solvent which is removed by evaporation
scribed is siven for illustration and is by blowins
after application and as extruded shapes such as
but other methods such as spraying the liquid
through an atmosphere of air or oxygen or ?ow
tubing for electrical insulation, for woven textiles
and for general use Where they are used in the
ing the liquid down'inclined surfaces in an at
dry state. And the compositions ofthe present 15 mosphere of air or oxygen can be used. By the
invention can be used in or with other materials,
for example, with arti?cial rubbers of the “Thio
kol" “Duprene” and “Buna” types to impart de
sired characteristics which are inherently lack
ing in the arti?cial rubber.
term “blown” as applied to any one of said sub
stances in this speci?cation and claims is meant
the product produced by subjecting the product
to free oxygen to thicken the same. This may be
. 20 done by following any one of the aforesaid speci?c
An object of the present invention is to provide
a plasticizer, or plasticising solvent, for vinyl
polymers whereby the vinyl polymers are modi
lied to produce dry compositions having rubber
25
like ?exibility and resiliency.
methods of blowing. spraying or cascading as
heretofore set forth.
Method for oxidation
The oxidation can be done by placing the liq
uid material to be oxidized (the terpenic products
Another object or the present invention is to
in liquid state) in a closed container having a
provide a modifying agent for vinyl polymers
conduit extending thereinto to apoint near the
whereby the resulting compositions can be used
bottom, with openings in the conduit for releasing
in arti?cial rubbers of the “Buna" or butadiene
types and other types, including “Thiokol” and 30 air or oxygen below the surface of the liquid '
therein. A vent is provided for releasing the air
"Duprene" to impart to said arti?cial rubbers
or oxygen to prevent too great pressure being
characteristics which are inherently lacking.
built up and to allow the air or Oxygen to circu
Another object of my invention is to provide a
late through the liquid. A stirrer is used to agi
plasticiser for vinyl polymers which plasticiser
can be used in comparatively large amounts or 35 tate the liquid being oxidized and thereby to in
crease the contact of the liquid with the air or
proportions, with respect to the amount of vinyl
oxygen. And heating of the liquid during blow
polymer used, and yet obtain a “dry” composition
ing is provided. In the illustrative method- the
in which the piasticiser is held in and from which
blowing is provided. In the illustrative method '
there is no bleeding of the plastiser, such large
proportion being, for example, as high as six parts 40 the blowing was done by air by the apparatus and
method described in this paragraph and at be
of the plasticiser to one part of the vinyl polymer,
tween about 160° F. and about 195° F. for about
by weight.
‘
twenty-four hours. the air when it reached the
The present application is a continuation in
treating apparatus being at normal or room tem-‘
part of my copending application Serial Number
45 perature. Rapid stirring of the liquid during
382,740, ?led March 11, 1941.
_
.
blowing was produced by revolving blades or pad
Illustrative examples of substances which can
dles. The volume of lfquid put in the vessel was
be blown to produce material suitable for the
about one-quarter of the capacity of the vessel so
practice of the present invention are methyl abie
that advantageous contact with the air was pro
tate (CmHzaCOOCHs), known on the market as
“Abalyn,” ethyl abietate, decyl abietate, phenyl 50 duced by the stirring.
By the term "terpenic products" as employed
abietate and the other hydrocarbon .abietates,
turpentine, pinene, pine oil, terpineol, dipentine,
in this speci?cation and claims. is meant the class
of products consisting of turpentine, pinene, pine
(limonene, for example), eucalyptol (as oil of
oil, terpineol, dipentine, eucalyptol (as oil of eu-‘
eucalyptus) and cedrene (in cedar wood oil).
calyptus) and cedrene (in cedar wood oil).
0! the substances mentioned in this paragraph,
2,409,270
4
3
serve to make the "Buna" and the vinyl polymer
Uses
compatible with each other and bring them to
The blown or oxidized terpenic products of the
gether into. a workable composition and at the
same time will not act deleteriously when the
present invention are useful in the arts generally,
and are useful particularly, for example, ( 1) for 5 composition is handled and worked into more
putting vegetable oils into solution with cellulose
advanced and ?nal states (as, for example, by
vulcanization through heating) but will remain a
nitrate, (2) as solvents for materials such as res
part of the ?nal composition either in its orig
ins of the glycerol-aldehyde resins, vegetable oils,
cellulose nitrate, cellulose acetate and ethyl cellu
inal form or in some intermediate or ?nal form.
Below is a table showing characteristics of
lose, (3) plasticising rubber, (4) ?oatation of ores, 10
mixtures of the starting solvents with a “Vinyl
and (5) aiding the solvent properties of soaps.
ite” resin and of oxidized solvents with the same
Another use is as a mutual solvent for arti?cial
“Vinylite" resin. The proportion is ?ve parts by
rubbers of “Buna” type and vinyl resins.
weight of solvent (or oxidized solvent) to one
The term “Buna" as used herein is intended to
mean certain synthetic materials made‘ from 15 part of "vinylite” resin. The “Vinylite” resin
used in each case is “Vinylite vyn w."
butadiene, with or without other materials, by
Characteristics of prod. mixed with "vyn w"
Characteristics of the mixtures
Product mixed 5 to 1 with
“vyn wll
pH
7
4
7
;
Blown plus 011....
.....
Dipentene _ . _ . . . . .
. . . ..
7
Blown dipentsne.
___._
Eucalyptus oil ............ ..
3-4
0
Eucalyptus oil, blown.
Cent. viscosity
Color
0.864/26...
1.027/25.-.
Water clean... Insoluble‘.
_
29
Soluble.
_
Soluble hot,
..
0.993/21 _
0.878/27 .
.
_
Wstsr clear...
Insol.
_..
.__
l6. ............. ..
Clear brown ..
Yellow clear.-.
Readily soLbleeds.
Soluble bleeds.
1.02/29 ............. .. Very heavy liquid.
Opaque ..... _.
_.
0.967/20 ............ _.
............. ..
Yellow clear...
Insoluble.
Heavier than water..
300,000+l27 ..... __
Opaque ..... ..
Soluble.
I ....... ..
comes
outcold
Brown green.. Partly sol. bleeds.
1.010/25
0848/21
Soluble.
Soluble, bleeds.
1.035/25.
Cedar wood oil, blown ....... ..
Cedar wood
.
4
Sp. gr. at °C.
.
Soluble.
polymerization or copolymerizaticn, to produce
The viscosity in each case was taken at the tem
perature shown for the corresponding speci?c
arti?cial rubber materials, for illustrative exam
gravity, and the factor of 4.75 used to multiply
ples, those known as and sold under the names of
the time in seconds of the ?ow of the liquid by
“Buna,” "Buna S," and “Perbunan" ("Buna N").
the centipoise method. The speci?c gravity was
“Buna” is a straight butadiene polymer; "Buna
taken with the hydrometer in each case except
S" is a copolymer of butadiene and styrene; and
in the case of “blown” “Abalyn" where it was
"Perbunan" ("Buna N") is a copolymer of buta
taken with the pycnometer. pH values were
diene and acrylonitrile; and the term "Buna” as
used herein is intended to cover also other buta 40 taken with Fischer pH paper.
Each of the “blown" solvents in the above table
diene polymers and copolymers of the “Buna”
was oxidized by the illustrative method described
type including products obtained by various poly
above for oxidizing terpenes and below are given
merization methods and steps and products ob—
examples of (1) a gel-like composition of blown
tained by copolymerising various proportions of
turpentine and a vinyl ester and (2) a “Buna"
materials such as various proportions of styrene
rubber mixture containing the gel-like composi
and butadiene or of acrylonitrile and butadiene
tions. Each of the other “blown” solvents in
and products obtained by copolymerizing other
the above table can be substituted for all or any
or different materials with butadiene such as oo
of the “blown” turpentine in the following exam
polymerizing coumarone or indene with buta
dlene and to cover generally arti?cial rubbers 50 ples.
Example 1.--A. One hundred parts by weight
which are butadiene polymers or copolymers.
of the "blown" turpentine described above are.
The term vinyl polymer is used to designate
heated to from about 150° C. to about, 165° C. and
polymers of vinyl esters such as polymerized vinyl
chloride, polymerized vinyl acetate, copolymers
of viny1 chloride and vinyl acetate, polymerized
twenty-?ve parts of polymerized vinyl chloride,
65 known on the trade as “vinylite qyna,” having
vinyl chloroacetate and other polymerized vinyl
esters. These range in consistency from the liq
uid state to solid resin-like products depending
a molecular weight of from about 20,000 to about
22,000, are added and stirred until solution takes
place. This is cooled and ready for various uses.
When cooled, this product is a rubbery mass, and
on the material and on the degree or extent to
which they are polymerized and are used in the 6.0 is a gel, and can be milled into the “Buna" type
practice of the present invention in their various }
arti?cial rubber, above identi?ed, to improve
aging, tear resistance and other physical prop
erties.
B. To a batch of the product described, in
ting them to use. For a number of uses such as 65 paragraph A, above, one hundred and twenty
?ve parts of "Buna S" were added and milled
in getting rubber-like gels with the "mutual sol
together on rubber-mixing rolls, together with
vent," before the “Buna” type rubber is incor
porated, vinyl polymers having molecular weights
nine parts of zinc oxide, ?ve parts of "Aminox,"
eight parts of "Toads," and one hundred and
between 20,000 and 30,000 are preferred. “Vinyl
ite-vyn w" has a molecular weight of about 24,000 70 ten parts of “Gastex." This produces a “rubber"
batch suitable for formation into various shapes
and "Vinylite qyna” has a molecular weight of
which can be vulcanized, for example, at 150°
from about 20,000 to about 22,000.
The mutual solvent or mutually compatible
C. for about ?fteen minutes in a pressure mold.
The examples of 5:1 mixtures of “blown” sol
vehicle for the “Buna" and the vinyl polymer of
the present invention is a material which will 76 vents disclosed above are given as illustrations of
states according to the use to which they are to
be applied and to the suitability of their consist
ency to the method of handling required in put
2,409,270
6
ten parts of vinyl acetate: "vyn f" which is a
the practice of the present invention, and these
mixtures are suitable for mixing into "Buns" type
arti?cial rubbers to give desirable characteristics
copolymer- of eighty-seven parts of vinyl chloride
and thirteen parts of vinyl acetate: "xyfg" which '
is polyvinyl butyral, formed by treating polyvinyl
to the latter. Some of the above mixtures are
alcohol with butyric aldehyde to give an acetal
called polyvinyl butyral which is soluble in butyl
alcohol and having a high tensile strength.
substantially dry to the touch, others are tacky
and still others are wet on the surface and some
‘of the “wet" bleed to greater or less extent. All
of them are gel-like in consistency and mill easily
An advantage or the compositions of the pres
ent invention is that they have a greatly improved
into rubber on rubber mixing rolls, and can be
made up into vulcanizable "rubber” compositions 10 tear strength or resistance as compared with
similar compositions made of ‘,‘Buna" type arti
?cial rubber without the vinyl polymers.
similar to that given in Example 13 above by
substituting any ofthe “blown” terpene products
In addition to illustrating the method of bring
ing arti?cial rubber-of the “Buna" type into solu
pentine of Example 1, above. Also, in each case 16 tion or compatibility with vinyl polymers, these
examples also illustrate the use of these solutions '
any of the preferred "Vinylite” resins can be used
of "Buna” type arti?cial rubber with vinyl poly
in place of "Vinylite qyna” and any of the "Buna"
mers in “rubber” mixtures or compositions suit
type arti?cial rubbers can be used in place of the
able for molding by heat and pressure or suitable
- “Buna S" of the examples. The proportionsof
ingredients in the “rubber” mixture are illustra 20 for sheeting in calender or sheeting rolls and for
general use to which rubber compositions can be
tive and variations can be made in practising the
placed.
art of compounding of “Buns.” rubber composi
The “Buna”-polyvinyl resin-mutual solvent
tions and any or the mixtures of any of the
compositions of the present invention can be vul
preferred “Vinylite" resins described herein with
any of the oxidized terpenes of the present inven 25 canized with sulphur alone or with various other
vulcanizers and can be used generally in the man
tion can be used in any of the "Buna” rubber
ner of rubber mixes as illustrated above in the
compositions described in my copending applica-.
examples given.
tion Ser. No. 382,740.
According to the present invention butadiene
Also for some purposes, whether for general use
or for making “Vinylite" gels for general use or 30 arti?cial rubbers are made to have characteris
tics and qualities which they do not have of them
for use in “Buna” rubbers the terpene products
selves and this by the addition of comparatively
can be oxidized (as by blowing with air or other
small quantities of polyvinyl resins having high
wise) while they are in mixtures with other ma
molecular weights, that is of the order of from
terials such as terpenes-Cl-hO reaction products.
For example, a mixture of equal parts by weight 35 about 20,000 to about 40,000, the addition being
disclosed above or any mixture of two or more
of them for all or any part of the "blown" tur
made through the medium of a mutual solvent
which is non-volatile up to at least 150° C. A
and turpentine was blown by the method above
number of the mutual solvents disclosed herein
described, also a mixture of equal parts of rosin
do not have boiling points at normal pressures.
and a condensation product of CHzO and turpen
tine; a mixture of equal parts of turpentine and 40 and cannot be distilled at normal pressures with
out decomposition.
'
>
.
CHzO-turpentine reaction product; and a mix
General examples of compositions of the pres-I
ture of equal parts of pine oil and CHzO-turpen
tine reaction product was blown by the same A‘ ent invention which illustrate the ratios of poly
vinyl ester, butadiene arti?cial rubber and mutual '
manner. In other cases CHzO-terpene reaction
products were blown with each of the unreacted 45 solvent are as follows:
of methyl abietate and a condensation of CHaO
terpenes named herein in proportions ranging
Parts by
weight
from 10 to 1 on oneside toil-t’ ' Dio'nthe. other
side, giving useful products.“ '
‘I
>
Any of the oxidized solvents of the present
invention can be heated to remove light volatiles 50
therefrom before mixing with the selected “Viny
Butadiene arti?cial rubber--.-
lite” resin to get desired states, of dryness, tacki
Polyvinyl ester.............. -.
Mutual so1vent_....; .............................. ..
A
B
O
75
00
5
20
2
. 8
ness or wetness to serve the purpose of its de
sired use. For example blown “Abalyn” was
heated up to‘ 240° C. to remove 10% of its weight 55 Generally the ratio of butadiene arti?cial rubber
to polyvinyl ester can be stated to range from
and blown dipentene was heated to remove 20%
about 50 to 1 to about 2 to 1, and the ratio of
of its weight and in each case they gave dry gel
mutual solvent to polyvinyl ester to obtain a gel
like mixtures with the “vyn w" in the proportions
like product can be stated to range from about
of 5 to 1 respectively. Also various proportions
of oxidized terpene-CHaO reaction product to 80 10 to 1 to 1 to 1. For melting the mutual solvent
and polyvinyl resin together the range is from
"Vinylite" resin can be used to serve desired pur
about 10 to 1 to about 2.5 to 1, and in the ratios
poses, for example, from about one part to about.
from about 2.5 to 1 to about 1 to 1 the two ingre
ten parts of the said oxidized terpene-CFhOre
dients can be brought together by milling them
action product to about one part of the “Vinylite”
65 into each other on rubber mixing rolls, the prod
resin.
ucts along the whole range (10 to 1 to 1 to 1) being
The following trade-mark names or trade
rubber-like gels.
Having thus described my invention, what I
claim and desire to protect by Letters Patent is:
names are ‘identi?ed as follows: "Gastex" and
“JP-33"‘ are carbon blacks; "Speedon," “Altax”
and “Tuads" are vulcanization accelerators: vand
“Aminox” is an antioxidant.
'
70
substituted for all or any part of the “Vinylite
vyn w" wherever that is used: "Qyna" which is
polymerized vinyl chloride; "vyn s" which is a
coplymer of ninety parts of vinyl chloride and
1. l The method which comprises heating to
gether from about one part to about ten- parts by
weight of a blown terpenic product with one part
of a polyvinyl ester to form a gel when cold.
2. A rubber-like composition comprising a poly
76 vinyl ester having a molecular weight between
In the examples above the following ‘can be‘ I
9,409,276
7
.
about 20,000 and about 40,000 and a blown ter
penic product.
'
3. A composition oi’ matter comprising buta
diene arti?cial rubber, a polyvinyl ester having a
molecularvweight 01’ at least 20,000, and a mutual
solvent which is non-volatile up to 150° C., said
being a blown terpenic product, the boiling point
of said mutual solvent being at least as high as
the mixing temperature, and then mixing in said
arti?cial rubber.
'
7. A gel of a polyvinyl ester and a blown ter
penic product, which said gel is compatible with
butadiene arti?cial rubber. .
butadiene arti?cial rubber being present in
8. A rubber-like composition comprising a poly
amount at least 50% by weight of the total of
vinyl ester having a molecular weight between
the three said components, and said mutual sol
10 about 20,000 and about 40,000 and blown turpen
vent being a blown terpemc product.
e.
‘
4. A rubber-like composition comprising a poly!
9. A rubber-like composition comprising a poly
vinyl ester having a molecular. weight between
vinyl ester having a molecular weight between
about 20,000 and about 40,000, a blown terpenic
about 20,000 and about 40,000, blown turpentine
product and a butadiene arti?cial rubber.
5. A composition of matter comprising buta 15 and a butadiene arti?cial rubber.
10. A composition or matter comprising buta
diene arti?cial rubber, a polyvinyl ester having a
diene arti?cial rubber, a polyvinyl ester having a
molecular weight of at least 20,000, and a. mutual
solvent which is non-volatile up to 150° C., the
ratio of said butadiene arti?cial rubber ranging
irom 2 to 50 parts for each part by weight of said
polyvinyl ester, said mutual solvent being a blown
terpenic product.
6. The method 01 making a compatible mixture
of a butadiene arti?cial rubber and a polyvinyl
molecular weight of at least 20,000, and a mutual
solvent which is non-volatile up to 150° C., the
ratio of said butadiene arti?cial rubber ranging
from 2 to 50 parts for each part by weight of said
polyvinyl ester, said mutual solvent being blown
turpentine.
‘ 11. A gel of a polyvinyl ester and blown turpen
ester which comprises mixing said polyvinyl ester 25 tine, which gel is compatible with butadiene arti
at about 150° C. with a material which is a mutual
solvent for said polyvinyl ester and said butadiene
arti?cial rubber to form a gel, said mutual solvent
?cial rubber.
MORTIMER T. HARVEY.
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