close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2406260

код для вставки
Patented Aug. 20, 1946.
2,406,260
UNITED} STATES PATENT OFFICE
2,406,260
POLYSULPHJDE POLYBIER
Laurence L. Ryden, Midland, vMich, assignor to
The Dow Chemical Company, Midland, Mich.,
a corporation of Michigan
No Drawing. Application December 3, 1943,
Serial No. 512,774
13 Claims.
.
(Cl. 260-78)
1
This invention is concerned with polysulphide
nearly resembles natural
2 rubber than organic
.
polymers and is particularly directed to a method
for the preparation of cold-?ow resistant organic
polysulphide polymers heretofore known.
,
The exact mechanics of the reaction are not
polysulphide polymers and to the polysuiphide
,
understood, and it is not desired that the inven
tion be in any way limited by theory as tohow
Organic polysulphide polymers have been sug
such result is accomplished. However, it seems
polymer product so obtained.
reasonable to assume that the provision of free
gested for use and found valuable in a Wide
hydroxyl groups along the chain oithe polymer
variety of applications. These materials are em
as initially formed'permits of coupling or cross
ployed in some instances as substitutes for nat
ural rubber and in others as distinct elastomer 1G. linking upon reaction with the unsaturatedpoly
basic acid or acid anhydride whereby a compact
products differing from rubber in. such a manner
molecule is obtained which is resistant to. defor
as to be preferable thereto. The cold-?ow prop
mation under pressure, a property not shared by
the conventional polysul-phide chain structures.
restricted their use. Thus thesematerials un
In carrying out the invention, the condensa
dergo deformation under pressure and show but
tion between the aqueous alkaline polysulphide
a slight recovery. This prohibits their use in
and organic reactant may be accomplished in
situations where high elasticity and resistance
any suitable manner, provided only that such
to flow are desirable.
reactants and amounts. be employed as yield a
A voluminous art has accumulated with respect
to the preparation of organic polysulphide poly 20 product of rubbery consistency. Thus the or
ganic reactant may be added all at once'to the v
mers. Rubber-like materials have been prepared
by reacting aqueous alkaline polysulphides with ' polysulphide solution or such addition may be
erties of the polysulphide polymers have greatly
a very wide variety of organic halides and‘ par
ticularly di-halo-alkanes such as ethylene chlo
ride, propylene chloride, and other aliphatic
portionwise with stirring to ‘accomplish “piece
meal reaction of ‘ the materials.
The temper
25 atures, concentrations, and‘other conditions 'of
reaction may be regulated as required. Similarly
‘the reaction of ‘the polysulphide polymer with
the polybasic acid‘ or anliydride coupling agent
may be accomplished in any suitable fashion.
issued December?, 1932; 1,923,392; issued August 30 Representative conditions of reaction for the
compounds containing -—CH2— radicals and a
multiplicity of halogen atoms. Representative
of the teachings of the art is the disclosure found
in United States Letters Patents Nos. 1,890,191,
condensation and coupling‘ or‘curing operations
22., 1933; Reissue 19,207, issued June 12, 1934;.
2,142,144, issued January 3, 1939; and 2,195,380,
issued March 16, 1940. Each of these patents dis
closes a large number of e'lastomer products all
subject to the disadvantages as outlined above
with respect to cold-?ow.
It is an object of the present invention. to pro
vide a method for the production of an organic
polysulphide polymer product which will be re
are set forth in U. S. Patent No. 2,195,380, ‘to
Joseph C. Patrick, dated March’ 26, 1940.
The preferred embodiment of theinvention re
sides in the use of glyceryl-dichlorohydrin in an
initial condensation with aqueous sodium poly
~
This chlorohydrin material» has» givenv
good results when employed in mixture with other
sulphide.
aliphatic halogen compounds-and particularly the
sistant to cold-?ow and deformation. It is a 40 lower alkylene halides. The amount of the glyc
eryl-dich-lorohydrin employed is between about 1
further object to provide .a such polysulphide
' and 20 mole per cent of the total organic react
polymer product which will have better proper
ant concerned. The balance of- the organic re
ties of recovery than characterize known polymer
actant consists preferably‘ of a mixture off-ethyl
products of this type. Other objects will become
apparen't'fr'om the following speci?cation.
I have discovered that a resilient polymer re
sistant to cold-flow is obtained by a modi?cation
of the usual procedure for the preparation of
ene, chloride and propylene chloride, with ‘the
former predominating. When too high a' propor‘
tion of glyceryl-dichlorohydrin is employed, the
polymer obtained does not have rubber-like prop
erties. When too little is used, the desired'cold
flow resistant characteristic is not obtained in the
organic polysulphide elastomers. This desirable
result’ is accomplished by carrying out the con
densation of the aqueous alkaline polysulp-hide
The- preferred coupling agent for reaction with
the basic polysulphide polymer is maleic anhye
with a mixture of’ (1) a halohydrin comprising two
dride. This reactant is employed in the amount Y‘
halogen atoms and at least one hydroxyl all
attached to aliphatic carbon atoms and (2)v other 55 of at least'5 per cent and preferably not‘ to ex
ceed 40 percent by Weight of the glyceryl-dii
polyhalo-aliphatic compounds to form an elasto
mer product, and thereafter reacting such prod
One mode of operation which has been found ’
uct with an alkenedioic acid or alkenedioic acid
particularly satisfactory consists of reacting. a
anhydride. The resulting material has good re
sistance to cold-?ow, and in this respect more 60 molecular excess of NazSLs-awith lI'mole‘ of; a
?nal
product.
chlorohydrin.
I
I
'
'
"
‘
-.
‘
'
2,406,260 7
.
3
,
V
.
elastomer in which onlyfone part Weight of
maleic anhydridewas employed. Here also there
mixture of glyceryl-dichlorohydrin and lower, al
kylene chlorides,the former beingpresent in the
was" obtained a'rubber-like material; ' ,
‘
amount of from about 5 to 20 mole per cent. The
reaction is carried, out by dissolving the polysulr. H ,Cylindrical plugs 1/2 inch high by 1/2
phide in water and adding the organic reactants "5 *in' diameter 'were prepared from the
elastomer. mixture and also from the
portionwise to the polysulphide solution with stir
ring at between 65° and 80f’_ c. Thepmixture ,i_s__ pomposition. in' mixture 'with 5 parts
'warmed and stirred at '70°-80° 1C. for janfaddi-7; hone‘;' part ‘of maleic ‘anhydride.
~ tional hour, and thereafter subjected ‘to treat- 7
ment with an aqueous solution of 0.2 mole of'a
" were fthenycured at 298° F. for
16 vvThese test
The
_
inch
basic
basic
and
plugs
15 minutes.
pieces‘ were employed to determine
high. ranking sodium polysulphide ~_(Na2S4.5 g-or _' the resistance to cold-?ow of the several mixtures.
In'ithis operation each plug was compressed to '75
per .cent of its original height for onerhour at
higher) at a temperature of between 785° and-110?’? .7 '
C.
The resultant latex is Washed with water,
a temperautre of 70° C. and the extent of recov~
coagulated with dilute acid, separated, and dried: ’ '
_While any suitable means may be employed to .15 cry of each determined upon the release of pres
react this initial elastomer product with the acid
or acid‘anhydride couplingagent, theipr'eferred
sure. From an initial‘ compressionto- 0.375 inch,
the "plug made ‘up from the unmodi?ed elastomer‘
vmethod consists 'of-mixing the product with'the
composition recovered only 2 per cent to a height
~ acid or anhydride on the rolls of a conventional
rubbericompounding mill. This is conveniently‘
accomplished by ?rst modifying the polysulphide
' of 0.377 inch. 'The plug preparedfrom the elas
20
tomer reacted with one part vof maleic anhydride'
recovered to the extent of 33 ‘per-cent tov 0.421
polymer product with additaments such as zinc
inch, and the plug made up from the elastomer
oxide,’ carbon black, and/or other ?llers,’ sta?
reacted with 57 parts of maleic anhydride recov
bilizers, and theilike, and then mixing and milling‘
thevcoupling agent ‘therewith. During" this and
_ ered to the extent of 62 per cent to 'a height of
0.453 inch. ‘A control plug prepared'irom a basic
the subsequent, step of curing at temperatures
composition containing an elastomer obtained by
the reaction of sodium polysulphide, withv the‘
above 250°; F., a reaction takes place between
the crude polymer product and the coupling agent _ alkylene'ha'lides in the absence of glyceryl-di
. chlorohydrin had 0 per cent recovery.
‘ x
whereby the desired cold-?ow resistant and re
silient polymermaterialis produced.
_
25
' V
. Example 2
The following examples illustrate the practice
Ina similar fashion a mixture of ‘6.9 parts‘ by
weight (0.06 mole) of propylene chloride, 69'
limiting.
,'
V
'
P
parts (07 mole) of ethylene chloridei and 22
35 parts (0.17 mole) of glyceryl-dichlorohydrin was
A mixture of '7 parts by weight (0.06 mole) of
reacted with a mixture of '94 parts by weightv (1_
of the. invention but are not to be construed as
-
.Egra’mplel,‘
_
.
.
' propylene chloride, '75 parts (0.76 mole) ofiethyl
mole) of NaZSLS, 2 parts of a sodium salt of sul
ene chloride, and 12 parts (0.09 mole) of 'glyceryl
dichlorohydrin was added portionwise and with
phonated ethyl oleate (Igeponap),§6 parts ‘of
freshly precipitated magnesium hydroxide,v and
stirring over a period of one .hour to a dispersion 40 500 parts of water. The initial reaction,'subse
in 500 parts of water of 94' parts by weight‘ (1.0
quent treatment with high'ranking' sodium poly-J
sulphide (Nazsfrs) , coagulatiomand separation all‘
mole) of Na2S1;5,'2 parts of'sodium-alkyl-naph4
thalene-sulphonic acid (Nekal BX), and '6 parts
were substantially‘ as described in Example ‘11
with therecovery of a substantial yield of dried
The temperature of the‘ reaction mixture‘ was 45 elastomer. 100 parts of
elastomer were com
maintained‘at' about 70’ C(during the addition‘.
pounded as follows:
'
v ‘, V
i
‘ ~
of "freshly precipitated magnesium hydroxide.
Stirringand warming of the mixture at 770°-80°
Material:
C. was continued for one hour. A'solution'of 38
_ '
Parts by weight
parts‘ by weight of Nagsit in 100 parts of water
Elastomer ____ __-__; _______________ __
was then added to the mixture and/stirring con
Carbon black ____________ __-e___-_______
tinue'd'for?an additional'hour, the temperature"
Stearic acid ___________ __- ______ __'____
0.5
mMercaptobenzothiaz'ole v__-___>___~_____‘_ .
‘2.0
,Diphenylguanidine 1____'_L___;_.____,__‘
0.1
.
being maintained at about 90° C. vThe resultant
' latex was washed several'times 'with'water and
coagulated with dilute sulphuricacid. 4 The‘ solid,
' i
The dried elastomer was then
the following basic mixture:
"
- '
60 -
' This basic composition was mixed with 5 parts‘
of maleic anhydride and cured-at 274° *F. for 1
product of reaction was separated’fro'm the'liquid
components of‘ the mixture and dried to- obtain
60 parts by weight‘ of ‘elastomer.
100
minutes
Cylindrical
to obtain
plugs awere
rubber-like
made upproduct.’
from the basic
.
'
elastomer mixture and from such mixture'fol
compounded in '
'
lowing- modi?cation with ‘maleic 'anhydride.
60 These plugs werev cured at 274°F. for 15 minutes
,-
~
and ‘subjected to compression as previously de
scribed.‘ The plug made up from the basic com
position showed a. 2 percent recovery to a height
Carbon "black _________ __:_ _________ __ .60}
0.377inch. The. plugfrom the modi?ed elas
vStearic acid _____ _'_ __________ __V_____-_ 0.5
Mercaptobenzothiazole ______ __-__;__; v2.0 65 tomer product recovered to a height of 0.465-inch,
Zinc~oxidegs____;s___s_e ____ _-_ ____ __‘
107.,
or,72
_ This composition‘ was then reacted:with"5‘part_s
by‘weight'of maleic anhydride by cold mixing ‘on
the rolls‘of a conventional rubber-compounding
mill and subsequent curing of the mixture for 15
minutes at 298° F. to obtain the desired‘rubber-v
like polymer product‘.
'
' A similar mixing and curing operation was car
ried out with an additional quantity of the dried
per cent.
7
_
'
,
I While the foregoing examples have been .di
rected speci?cally to operations in which the
cross-linking or coupling is accomplished. with
70
maleic anhydride, it‘ is to be understood that
equivalents therefor may also be employed. Rep
resentative of the acids and anhydrides poten-J
tially adapted for'such use are maleic acid, citra
conic acid and; anhydride, glutaconic acid and
anhydride,
pyrocinchoninic
acid . anhydride,
2,406,260
6
ethyl maleic acid and anhydride, methyl ethyl
from about 5 to about 40 per cent by weight
maleic acid and anhydride, xeronic acid and an
of the
hydride, methyl glutaconic acid and anhydride,
etc. Also other polyhalo-aliphatic compounds
thereafter heating the mixture to obtain the de
sired rubber-like composition.
may be substituted, wholly or in part, for the
ethylene chloride and propylene chloride dis-'
polysulphide polymer product prepared accord
6. A cold-?ow resistant rubber-like organic
ing to the process of claim 5.
7.‘ A method for the preparation of cold-?ow ,
closed. Representative of such materials are bu- '
tylene chloride, B,B’-dichlorodiethyl ether, 1.3
trimethylene chloride, dichlorobutylene, etc.‘
I
claim:
.
glyceryl-dichlorohydrin employed,_ and -
resistant rubber-like organic polysulphide poly
10 mers, which includes the steps of condensing a
'
1. A method for the preparation of cold-flow
resistant rubber-like organic polysulphide poly
molecular excess of an alkaline polysulphide with
a mixture of (1) from 1 to 20 mole per cent of
a halohydrin comprising two halogen atoms and,
mers, which includes the steps of condensing .a
molecular excess of an alkaline polysulphide with
at least‘ one hydroxyl all attached to aliphatic
a mixture of (1) from 1 to 20 mole per cent of a 15' carbon atoms in (2,) a polyhalo-aliphatic com
halohydrin comprising two halogen atoms and’
pound containing at least one —CH2- radical,
.to form an elastomer product, thereafter com
carbon atoms in (2) a polyhalo-aliphatic com-‘
pounding such product with one of the group .
pound containing at least one -—CI-I2 radical to
consisting of alkenedioic acids and anhydrides
form an elastomer product, and thereafter com 20 in the amount of from about 5 to, about 40, per
pounding such product with one of the group
cent of the halohydrin employed, and heating the
consisting of alkenedioic acids and anhydrides in
mixture to obtain the desired rubber-like com
the amount of from about 5 to about 40‘ per cent
by weight of the halohydrin employed.
.
'
8. A method for the preparation of cold-?ow
2. A method for the preparation of cold-?ow 25 resistant rubber-like organic polysulphide poly
resistant rubber-like organic polysulphide poly
mers, which includes the steps of condensing a
mers, which includes the steps of condensing a
molecular excess of an alkali-metal polysulphide
at least one hydroxyl all'attachedto aliphatic
position.
molecular excess of an alkali-metal polysulphide
with a mixture of (1) from 1 to 20 mole per cent
-
v
'
with a mixture-of (1) from 1 to 20 mole per cent -
of glyceryl-dichlorohydrin in (2), a lower alkyl
of glyceryl-dichlorohydrin in (2) a lower alkyl 30 ene halide to form an elastomer product, there
after compounding such product with one of the
ene halide to form an elastomer product, and
thereafter compounding such product with one‘
group consisting of alkenedioic acids and anhy-J,
drides in the amount of from about 5 to about ’
of the group consisting of alkenedioic. acids and
40 per cent by weight of the glyceryl-dichlorohy-'
V
anhydrides in the amount of from about 5 to 40
per cent by weight of glyceryl-dichlorohydrin
drin employed, and heating the mixture to ob- ' ‘
employed.
,
I
3. A method for the preparation of cold-?ow
resistant rubber-like organic polysulphide ,poly
i ‘ tain the desired rubber-like composition.
9. A method for the'preparation of cold-?ow
resistantrubber-like organic polysulphide poly
mers, which includes the steps of condensing a
molecular excess of sodium polysulphidewlth a 40 molecular excess of sodium polysulphide with a
mixture of (1) from 1 to 20 mole per cent of
mixture of (1) from 1 to 20 mole per cent of
glyceryl~dich1orohydrin in (2) an alkylene hal
glyceryldichlorohydrin in (2) an alkylene halide
product consisting of about 90 per cent ethylene
ide product consisting of ab0ut90 per cent ethylg
ene chloride and about 10 per cent propylene
chloride and about 10 per cent propylene chlo
chloride to form an elastomer product, and
ride to form an elastomer product, thereafter
compounding such product with an alkenedioic
thereafter compounding such product with an
alkenedioic acid anhydride in the amount of
acid anhydride in the'amount of from about 5
to about 40 per cent by weight of the glyceryl-di
from about 5 to 40 per cent by weight of‘g1ycery1
mers, which includes the steps of condensing a '
chlorohydrin employed, and heating the mixture
' 1
'
4. A method for the preparation of cold-?ow 50 to obtain the desired rubber-like composition,
resistant rubber-like organic polysulphide poly
10. A method for the preparation of cold-?ow
mers, which includes the steps of condensing a
resistant rubber-like organic ‘polysulphide poly
molecular excess of sodium polysulphide with a
mers, which includes the steps of condensing a
mixture of (1) from 1 to 20 mole per cent of
‘molecular excess of sodium polysulphide with a
glyceryl-dichlorohydrin in (2) an alkylene hal
mixture of (1) from 1 ‘to 20 mole per cent of
ide product consisting of about 90 per cent ethyl
glyceryldichlorohydrin in (2) an alkylene halide
ene chloride. and about 10 per cent propylene
product consisting of about 90 per cent ethylene
dichlorohydrin employed.
chloride to form an elastomer product, and
thereafter compounding such product with ma
leic acid anhydride in the amount of from about
5 to 40 per cent by weight of glyceryl-dichloro
hydrin employed.
5. A method for the preparation of cold-flow
resistant rubber-like organic polysulphide poly
mers, which includes the steps of condensing a
molecular excess of sodium polysulphide with a
mixture of (1) from 5 to 20 mole per cent of
glyceryl-dichlorohydrin in (2) an alkylene hal
chloride and about 10 per cent propylene chlo
ride to form an elastomer product, and there
after compounding such product with maleic
acid anhydride in the amount of from about 5
to about 40 per cent by weight of the glyceryl-di
chlorohydrin employed, and heating the mixture
to obtain the desired rubber-like composition.
11. A cold-?ow resistant rubber-like organic
polysulphide polymer product prepared accord
ing to the process of claim '7.
a
12. A cold-?ow resistant rubber-like organic
ide product consisting of'about 90 per cent ethyl
polysulphide polymer product prepared accord
ene chloride and about 10 per cent propylene
ing to the'process of claim 9.
chloride to form an elastomer product, mixing
this elastomer with carbon black and vulcaniz
13. An uncured organic polysulphide elas
tomer product prepared according to the proc
ing accelerators, mixing with such elastomer
composition maleic anhydride in the amount of
ess of claim 1.
'
LAURENCE L. RYDEN'.
Документ
Категория
Без категории
Просмотров
0
Размер файла
568 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа