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Патент USA US2408378

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Patented Oct. 1, 19,46
2,408,377 *
PATENT OFFICE-*2 "
2,408,317 -,
'
POIQYXINEYL *ALQQHOL COBIPGSI-TIO‘NI'E 1'1" '
ohaneanahgemajer,nuueyaN. .17.; assignor to
Reds‘ist‘o?ex Corporation, Belleville, N. J ., a cor
porationmf‘New vYoi'k
NmiDrawingzaApnlication
Serial No. 4415275
May
a942,;
.
This invention relates to plastic..compositions,
forms may‘be“madei'bytmoldin'g;"extrudingrdipv »'
and.moreparticularly.tocQmDositions.comprising
ping‘andmtherpro cedures, 'from‘pla‘stieized com-e" -
positions" of“ polyvinyljalcohol: >‘ 'Su'ch" composi~¢~
polyvinylrender‘- thealcohol
-c ompositio‘iishnormallyl
land. .modifying..agentsaivhich.
?exible... The -_~ tion's“ may~also~contain ?lling; ‘coloring’ and other“
compositionsaofethé.presentiinvention are. an.im;-... 5 ; ,m'odifyin‘g eingredientsfifi desired. " The'wternr'fr
“p'olyvinyt alcohol? is 'rusedr-hereinan'd ~-‘in ether’
provement._ov.er.~_known compositions» of. this kind
claims to"designatenot-'onlylgenerically pureipoly-‘c
vinyl- alcohol; Which'may» bé'obtained “in-"various
modi?cationw'but “also 'such‘fpartial "derivatives";
with..resnect...to§ their _-retention of. ; ?exibility-pt. ..
sustained elevated temperatures.
.
.
Plastic. polyvinyl alcohol compositions are suit
ablel-for theamakingiofm?exibleltubes,..hose,.-gasal. 10, th’e'reof’as contain a sufficientsnumbenof=unsubi~'=_~
kets, washers, diaphr'agms, .~ ?lnis, ...sheets,'... ?la'a.» stituted- -hydroxyl"_ groups as‘ to*“ren'dei~‘*the ‘com-r‘ ‘
poun'dlsolublein'fwaterr" For‘a fuli'e'r’explaiiatiomw
merits, _coati-ngs._.and .thé-likéa -...Tli'éy rareparticul
see PatenteNof 2,11 1,2722 orPaulM5'Paulsorryissued- ‘
larly.suitableIfor use inlthe. handling. ..of..hydro.-..
March1~>1~5§ L1938iii ,Theipoly'vi-nyl ialco'ho'l?used *in‘
15. thé'follo'tvin‘g examples was ‘one’-of"medi1lm“sa'-*~
carbon fuels; .oils‘i'and?ianyi.organicisolventsg by»;
which thénareunaffééted.
It ‘is . ‘particulai‘ly‘?e'sirahl el'ihaa articles; made}...
vinyl alcohols which-are *not'completely' saponi?e
binations
The examples/‘given
of ingredients,below
apart‘contain’
from the
novel
chlorides“
lcom
Heretofore. .normally. ?exiblelanti'cles'fsofa plastic '
polyizinylalcohol compositions..have~hardened,or. .20. referred -to,<_whichfare'not' claimed herein‘ asth‘ey
become. brittle when subj'e'cted...to.' elevated..tem.-.. are the‘ subject matter 'of-my copen'din‘g-applica?
peratuites. “for ,extended..periods. of.;.ti1rie,.. assfoi'a. tion Serial ‘~No‘5-34'6j150f now"Patent=No?~'2,340;866i'~E
of such ,Izompositiohs shalllretaingtheh- desirable Ia
?exibility‘ throughout a wideltemperature rangea.
example, inthe case of a ?exible ‘tubing. usedatow
convey.lubrica.ting.oil.in.~_.anaenginaa'.
.
'
issued'-February*8, 1-1 94495 ‘
"
Aceordingl-tmthe present inventionrepolyvinyl"
'I'liemhj'eg'atb?ilié .pres'entiinventionaistto. imaagr; ‘alcohol “is? mixed *With‘ivvatefrplasticizermhmetal “
prove the physical pronerties.-.of .compositions. of... ;
the'_.type describedgandmparticularly ,todncreaset...
their‘ ability'to withstand high temperatu'iiesivithe;v ’
out losing. their?exibilitym
'
‘
chlorideilandk otherlin‘gredientsj‘if “any; to‘ provide‘ "
a materia-lr'suitable "for-‘working up; intol'?n'ished‘v *‘
articles by any desired process. The metal salt“
is ‘disselvedsin-ithe ‘waters and1~added-“to~‘ the)‘, other
In"‘my Patent NoI"2,2'4"6;9l'5' I have disclosed 30~ingrediéiitshirr solution.“- In‘ltlie examples?"thejc
that the incorporation in ?exible polyvinyl alco
hol compositions of the water soluble haloids of
ammonium, of thealkali metals and of the alka
line earth metals greatly improve the stability
of the compositions at elevated temperatures. 1, 35
have now made further discoveries with respect
to other materials which give even better results.
f ormula'e-agive imixesesuitaable'iioii'ruse' ineaccorden-v
ance with the process described in Schnabel Pat
ent No. 2,177,612. After mixing, the ingredients
are passed through rolls to form the material into
strips. The temperature of the rolls may be
varied within wide limits (15°-90° C.) depending
upon the water content, the nature of the poly
vinyl ‘alcohol, the thickness of the strips, and on
the ingredients of the composition. The strips
40 may then be converted by extrusion or molding
procedures into any desired form.
In accordance with thepresentinvention it
has been discovered that the incorporation in
?exible polyvinyl alcohol compositions of certain
metal chlorides greatly increases their stability
To more particularly described the invention
and increases the duration of their ?exibility at
and to enable those skilled in the art to practice
elevated, temperatures. Experiments with a large
it, the following speci?c examples are given by
number of metal salts resulted in the surprising
discovery that unique effects were produced by 45 way of illustration:
chlorides of aluminum and tin.
Example 1
The effectiveness of the aforementioned chlo
rides with different polyvinyl alcohol composi
A composition was prepared from the following
tions has been experimentally established and
they have been found to be generally useful for 50 ingredients: ‘
Parts by weight
increasing the duration of ?exibility of such com
positions at elevated temperatures. This e?ect
Polyvinyl alcohol _______________________ __ 100
is referred to herein as “thermostabilizing” and
Glycero1 _________________-___;___________
the means'for effecting it as “thermostabilizing
agents.”
55
Formamide
As is already known, ?exible articles of various.
Water ___‘
‘
y
35
6
___
40
Aluminum chloride ..____‘ ___________ __‘___.__
8
2,408,377
4
3
The aluminum chloride used was AlCls?HzO‘. It
was ?rst dissolved in the water, admixed with
the glycerol and formamide and the resulting so
lution was then evenly distributed in the dry
powdered polyvinyl alcohol which was thereafter
processed to provide molded sheet material for
test purposes.
many kinds of apparatus, equipment and ma
chinery in the form of hose, tubing, gaskets, dia
phragms, coatings, packing and the like. Such
parts may be used in pumps, valves, hydraulic
systems, internal combustion engines, various
kinds of machinery, etc. In such applications
it may be required that the polyvinyl alcohol com
'
positions withstand continued high temperatures,
Example 2
A molded composition was formed as in Ex
as for example when parts formed from such
compositions are part of the lubricating or fuel
ample 1 from the following ingredients;
Parts by weight
supply system of an engine. By increasing the
Polyvinyl
alcohol _____________________ _ _
100
Glycerol _____________________________ _ _
35
Formamide
__________________________ _ _
6
duration of ?exibility or the stability of the com
positions at elevated temperatures, their range
of usefulness is greatly increased and they are
15 rendered adaptable to various ?elds in which it
has not hitherto been practical to use them.
The invention is not limited to the detailed ex
amples herein given by way of illustration but may
The stannous chloride used was SnCla2HzO.
be modi?ed in various ways within the purview
Test strips of the materials of the foregoing
of the claims.
20
examples were tested for their resistance to sus
Water
______________________________ _ _
Stannous
chloride ____________________ _ _
40
8
tained high temperatures by submerging them in
an oil bath maintained at a temperature of 124°—
126° C. They were removed at 24 hour intervals
and bent 180 degrees around a rod of %” di
What is claimed is;
.
1. A normally ?exible plasticized polyvinyl al
cohol composition containing as a thermostabiliz
ing agent a substance selected from the group
ameter, once in each direction, and. then returned 25 consisting ofrthe chlorides of aluminum and tin.
2. A normally ?exible plasticized polyvinyl a1
cohol composition containing as a thermostabiliz
Using as a basis of comparison the composition
ing agent aluminum chloride.
of Example 6 of my Patent No. 2,246,915, in which
3. A normally ?exible plasticized polyvinyl al
the thermo-stabilizing agent was ammonium
chloride, the results were as follows: the material 30 cohol composition containing % a thermostabiliz
ing agent stannous chloride.
of Example 1 was equal to that of said Example 6
4. A normally ?exible plasticized polyvinyl al
in duration of ?exibility but was superior to it in
cohol composition containing as a thermostabiliz
that the material of Example 6 blisters badly at
ing agent a substance selected from'the group
a temperature of 150° C. while the material of
consisting of the chlorides of aluminum and
Example 1 does not form blisters at that tem
tin; said substance being present in an amount
perature; the material of Example 2 had a dura
su?icient to increase/the duration of ?exibility at
tion of flexibilityptwice as long as that of Ex
to the bath unless bending produced fracture.
ample 6.
~
.
.
While-the examples give the quantity of metal
elevated temperatures.
7 _
5. A'normally ?exible plasticized polyvinyl al
chloride in each case as 8%, based on the weight 40 cohol composition containing as a thermostabiliz
ing agent from about 3% to about 15% of alu
of the polyvinyl alcohol, the quantity may be
minum chloride, calculated on the amount of
varied within a range of from about 3% to about
polyvinyl alcohol. '
'
15%, for practical results. In genera1 the ther
6. A normally ?exible plasticized polyvinyl al
mostabilizing effect increases with an increase in 45
cohol composition containing as a thermostabiliz
the amount of the chloride. The best results with
ing agent from about 3% to about 15% of stan
stannous chloride have been obtained with abou
nous chloride, calculated on the amount of poly
12%,
i
vinyl alcohol.
‘
.
The practical advantages of the present inven
CHARLES DANGELMAJER.
tion are many. Polyviny1 alcohol compositions 50
have varied applications in industry as parts of
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