Note: Descriptions are shown in the official language in which they were submitted.
76 ,557 CA~I/JVL
--1--
EIYDROXYL--TERI~I~IATF:D
POLY(HALOALKYLENE ETHERS)
This invention is related to hydroxyl-terminated
poly(haloalkylene ethers). More particularly it i5
related to hydroxyl-terminated poly(haloalkylene ethers)
wherein the halogen atoms are pre~era~ly bromine c~r
chlorine, to processes LOr the1r preparation, and to novel
catalyst systems use-Eul in saic3 processes. In the case o
hydroxyl terminated poly(chloroalkylerIe ethers) the
products are substantially colorless.
For the purposes o~ convenience, the hy-3roxyl-
terminated poly(haloalkylene ethers) are sometimes
referred to hereinafter as polyols. For purposes of this
disclosure, the term "polyols" includes materials which
have at least one terminal hydroxyl group.
Hydroxyl-terminated poly(haloalkylene ethers)
and processes for their prepartion are known. Frequently
the processes utilize cationic polymeri~ation techniques
wher~in oxirane monomers (e.g. 7 alkylene oxides, alcohols
and acid catalysts are employed to synthesize hydroxyl-
functional prepolymers. Thus, for example, see United
States Patents 3,850j856; 3,910,878; 3,910,879, and
3,g80,57g.
The products described in these patents have not
proven entirely satisfactory. For example, it has been
found very difficult to control the temperature of the
polymerization during their preparation. Additionally,
the chloroalkylene products are dark in color and tend to
be very slow to react with various materials (such as
isocyanates~ unless substantial ~uantities oE catalysts
are employed. Furthermore, these products have been found
to be unstable when exposed to light (e.g., sunli~ht) and
heat (e.g., temperatures above 50C). Thus, they become
even darker in color and increase in acidity and water
content when exposed to such conditions. Still further
the hydroxyl-terminated materials described in United
~J~
--2--
States Patent 3,980,579 adversely afEect the catal~tic
activity of amine catalysts utilized in ~he preparatiorl of
polyurethane Eoam.
Other techniques for the preparation o
hydroxyl-terminated poly(haloalkylene) ethers are also
known, Thus, U.S. Patent 3,450,774 teache3 the
preparation of hydroxyl~terminated polymers hy the
cleavage of high molecular wei~ht, cryst.-lLIinQ
poly(epihalohydrin) in the pre~sence oE ce~tain ;I]kali
compounds. The resulting polymers are cry3t~llLin~ and
have low molecular weic3ht. Moreover, these polylne~; are
only partially hydroxyl functional. trhus, t~ley ~ay have
carbonyl and ethynyl end groups in place of the hydroxyl
end groups~
Other poly(haloalkylene ethers) are clescribed in
U.S. Patents 3,636,163 and 3,850,857. The former patent
describes the reaction of epibromohydrin and a phosphorous
compound in the presence of a Friedel-Crafts catalyst.
The latter paten~ describes the polymerization of epihalo-
hydrin in ~he presence of a catalyst of a trialkyl onium
salt or HMF6 wherein M is a Group V element.
The present invention provides novel hydroxyl~
terminated poly(haloalkylene ethers), processes for their
preparation, and catalyst systems useful therein. The
chloroalkylene ethers of the present invention represent a
preferred class of mat~Qrials that is optically clear and
colorless. Thus, the chloroalkylene ethers appear to have
the same optical clarity as distilled water~ Moreover,
they exhibit a color magnitude (described more fully
hereinafter) of less than about 10. Additionally, they
are stable to the effects of heat and light (i~e., they
resist degradation due to such conditions) and they
possess excellent chemical reactivity ~ith isocyante
materials.
The poly(chloroalkylene ethers) are particularly
useEul where the color o the 1Einished product is
important (e.g., where the true color of the product is
--3--
critical). Thus, for ex~mple, they are particularly
useful in tne preparation of cast urethane syste~ns ~lhich
can be used for such things as floor1n-J materials,
coatings, and adhesives. ~oreover, the urethanes pro~3uced
with the polyols of the invention have be~n found to
exhibit improved properties over prior a~t urethanes.
Thus, or example, .such urethanes exhi~it excellent
resistance to grease and oiL.
In accordance with the p~e/(-nt invent1O~I th~r(?
are provided amorphous, hydroxyl-terlnirlatecl
poly(haloalkylene ethers) havin~J the ~ormula
R5~o
wherein Rl and R2 are each selected from
hydrogen and methyl; R3 and R4 are selected from hydrogen,
lower alkyl groups containing from 1 to 10 carbon atoms,
and lower haloalkyl groups containing from 1 to 2 carbon
atoms and ~rom 1 to 5 halogen atoms, provided that at
least one of R3 and R4 is said lower haloalkyl group~ X5
is the residue of hydroxyl material which contained from 1
to 6 hydroxyl groups; b is an integer of from 1 to 50; and
d is an integer oE from 1 to ~.
Preferably the polyols of the invention are
poly(bromoalkylene ethers) or poly(chloroalkylene ethers).
The poly(chloroalkylene ethers) preferably contain from
about 20g to 60% by weight chlorine.
The poly(haloalkylene ether) polyols of the
present inven-tion are amorphous materials. Thus, they do
not exhibit a melting point. Moreover, they may vary rom
low molecular weight (i.e., about 250 MW) to high
molecular weight (i.e., about 5000 MW) materials based
upon the average hydroxyl functionality oE the polyols.
Also provided is a novel two cornponent catal~st systc~n use~ul in the
preparation of the polyols. It comprises
(i) HF; and
(ii) a polyvalent tin compound havlny th~: Eonnu:La
~6
~5 1 _~7
(1~,
wherein g is 0 or 1; R and R are tlle catne or d.i.~ e~ent and a~f~ '`Je.leCted ErOIII
saturated and unsaturated aliphatic and aromatic hydrocclrbyL g~oups cOntaininCJ
from 1 to 10 carbon atoms; R is selected Erom the yroup COIlSiStiny of oxygen
and saturated and unsaturated aliphatic and aroma tiC hydrocarbyl yroups contain-
ing from 1 to 10 carbon atoms, provided that when R is oxygen then g is 0i and
R is selected from the group consisting of fluorine, acyloxy groups containing
less than 10 carbon atoms, and
IR5 6
O - Sn - R
The molar ratio of the polyvalent tin compound to the HF is in the
range of 1.13:1 to 3:1O Preferably -this ra-tio is in the range of 1.2:1 to 2:1.
Still further there is provided a method of makiny the polyols of the
invention utilizing the novel catalyst system wherein a hydroxyl containing
material having from 1 to 6 hydroxyl groups is combined with an alkylene oxide
and polymerized in the presence of the above-described catalyst SyStenl.
The hydroxyl-terminated poly(haloalkylene ethers) of the invention are
prepared by combining the hydroxyl-corltaining material, the alkylene oxide (at
least about 50% by weight of which is haloalkylene oxide), and the catalyst
system of -the inven-tion, and polymerizing the resultant mixture. Polymerization
may be carried out at a -temperature in the range of about 0 C to 110 C. PreEer-
9~3
ably polymerization is carried out at a temperature in the range of about 40 C
to ~0C.
Solvents may be employed during polymeri7ation. They are especially
useful when one or more of the ingredients of the mixture :is a isolid. Suitable
solvents solvate (but are otherwise inert to) the materials in the
~ 5 -
,i i i`
llh~3
--6--
mixture. Representative examples oE ~uitable solvents are
benzene, toluene, methylene chloride, carbon tetra-
chloride, and l,2-dichloroethane.
Although the polymerization proceeds smoothly to
cornpletion, there may be some unpolymerized h~loalkylene
oxide left. This material may be separated from the
poly(haloalkylene ethers) of the invention by warming the
polymerization mixture (e.g., to 80C) and subjectiny the
heated mixture to reduced pressure ~e.g., 0.01 Torr) fo~ a
short period of time (e.y., 1-2 hours).
A wide variety o~ hydroxy1-containing rnaterials
are useful in ~he present invention. They include, eor
example, water, and liquid an~ solid organic materials
which have a hydroxyl functionality of at least one. The
organic materials may be monomeric or polymeric and are
preferably selected from mono- and polyhydric alkanols,
haloalkanols, and polymeric polyols.
The hydroxyl groups of the organic materials may
be terminal or pendant (i.eO, other than terminal) groups.
Hydroxyl-containing materials containing both terminal and
pendant hydroxyl groups may also be used. The molecular
weight of the organic hydroxyl-containing material may
vary over a rather wide range. For example it may be in
the range of from 10 to 2,500.
Pref~rably, the organic hydroxyl-containing
material is an aliphatic material which contains at least
one primary or secondary aliphatic hydroxyl group (i.e~,
the hydroxyl group is bonded directly to a non-aromatic
carbon atom). Most preferably said organic material is an
alkane polyol.
Mono- and polyhydric alkanols useful in the
present invention include methanol, ethanol, isopropanol~
2-butanol, l-octanol~ oc~adecanol, 3~methyl-2-butanol,
5-propyl-3-hexanol, cyclohexanol, ethylene glycol,
propylene glycol, 1,3-butanediol, 1,4-butanediol,
1,6 hexanediol, 1,4-cyclohexanedimethanol, glycerol, and
sorbitol.
--7--
Mono- and polyhydric haloalkanols use~ul in the
present inventon include 2-chloroethanol,
3-chloropropanol, 2,3-dichloropropanol,
3,4 dihromo-1,2-butanediol, 2,3-dibromo-1,4-butanediol,
and 1,2,5,6-tetrabromohexane-3,4-diol.
Polymeric hydroxyl-containiny materials useful
in the present invention lnclude polyoxyethylene and
polyoxypropylene glycols and triols o~ molecul~r weights
from 200 to 2000 ~correspondin~ to hy~roxyl e~uivalerlt
weights of 100 to 1000 for ~he cliols and 70 ~o 630 Eor
triols); hydroxy-terminated polyalkadienes; and
polyte-tramethylene glycols o varying molecular weight,
such as the Polymeg~ series of glycols available from
Quaker Oats Company as Polymeg~ 650, 100~, and 2000.
The foregoing list oE useEul hydroxyl-containing
materials is intended to be illustrative only. Still
other hydroxyl containing materials are also useful as
will be clear as a result of this disclosure.
The exact hydroxyl-containing material selected
for use in the presen~ invention is dependent upon the
terminal hydroxyl functionality desired in the
poly~chloroalkylene ether) polyol. It has been found that
the polyols of the invention have the same hydroxyl
functionality as that of said hydroxyl-containing starting
material and that the hydroxyl-functionality is present as
a terminal hydroxyl group. Thus, for example, when a
monofunctional hydroxyl-containing material is used~ a
monohydric polyether is obtained; when a difunctional
hydroxyl-containing material is used, a dihydric polyether
~olyol is obtained; etc~
Mixtures of hydroxyl~containing compounds may be
used if desired. For example, one may use mixture of two
or more poly-functional hydroxyl compounds, one or more
mono-functional hydroxyl compounds with one or more
polyfunctional hydroxyl compounds, etc.
A wide variety of haloalkylene oxides are useful
in the present invention. They include, for example,
-8-
epichlorohydrin, epiromohydrin,
l-chloro-2-methyl-2,3-epoxypropane,
1,4-dibromo-2,3-epoxybutane, 1,4-dichloro-2,3-epoxybutane,
l-bromo-2-methyl-2,3-epoxybutane, and
1-chloro-2,3-dimethyl-2,3-epoxy-butane. More highly
halogenated monoalkylene oxides are also useful in the
present invention. Representative examples of these
materials include l,l-dichloro-2,3-epoxypropane,
1,1,1-trichloro-2,3-epoxypropane,
1-bromo-1,1-dichloro-2,3-epoxypropane,
1,1-dichloro-1-fluoro-2,3-epoxypropane,
1,1-difluoro-1-c~lloro-2,3-epoxypropane, etc. Stil:L other
useful haloalkylene oxides include
1,1 dichloro-2-methyl-2,3-epoxypropane,
1,1,1-trichloro-3,4-epoxybutane,
1,l~dichloro-3,4-epoxybutane,
1,1,1,2,2-pentachloro-3,4-epoxybutane,
1,1,1,4,4-pentachloro-2,3-epoxybutane, 1,1,1,2,2-mixed
pentahalo-3,4 epoxybutane and
1,1,1,2,2-pentachloro-2-methyl-2,3-epoxybutane.
Tetrachloroepoxybutanes such as
1,1,4,4-tetrachloro-2,3-epoxybutane,
1,1,2/2 tetrachloro-3,4-epoxybutane and
1,1,1,2-tetrachloro-3,4-epoxybutane may also be sued.
Mixtures of any of the foregoing haloalkylene
oxides can be used as well as mixtures of at least one
haloalkylene oxide with up to 50% by weight of one or more
non-halogenated alkylene oxides. Exemplary of useful
non-halogenated alkylene oxides are propylene oxide,
l~hexylene oxide, cyclohexane oxide, styrene oxide, methyl
glycidyl ether and phenyl glycidyl ether.
By controlling the proportions of alkylene oxide
to hydroxyl-containing material, it is possible to limit
the degree of addition and, consequently, the molecular
weight of the polyols of the invention. Thus, the molar
ratio of alkylene oxide material to hydroxyl group in said
hydroxyl-containing material may he in the ran~e of 1:1 to
_9_
S0:1 preferably the molar ratio i5 in the range o~ 1:1 to
20-1.
Catalyst systems useful in the present invention
comprise (i) a fluorinated ~cid selected from the group
described above and (ii) a polyvalent tin compound as is
described above. As little as 0.05~ by weic3ht o~ the
catalyst system based on the combined weight o~ the
hydroxyl-containing material and allc~lene oxi-1e is
effective in providin~ the polyols o~ the invention~
As discussed above, the molar ratlo of the
polyvalent tin compound to the fluorlnated acid is
dependent upon which fluorinated acid is em~)loyed in the
catalyst system. However, whatever the exact ratio used
is, the catalyst system may be easily prepared by simply
adding each of the ingredients to the polymerization
mixture.
As has been previously s~ated, the fluorinated
acid useful in the catalyst system is selected Erom the
group consisting of bis(fluorinated aliphatic sulfonyl)
alkanes, HF, and acids of the formula HmXFn~m. The
bis(fluorinated aliphatic sulfonyl) alkanes are preterably
highly fluorinated alkanes containing from 1 to 15 carbon
atoms~ Additionally, they include compounds which
liberate such alkanes in the presence of heat or moisture.
For example, bisthighly fluorinated alkylsulfonyl)alkenes,
upon hydrolysis~ will yield bis(highly fluorinated
alkylsulfonyl~alkanes.
As it is used herein, the term highly
fluorinated aliphatic radical encompasses Eluorinated,
saturated, ~onovalent, aliphatic radicals having 1 to 10
carbon atoms~ The skeletal chain o the radical may be
straight, branched or, if sufficiently large (e.~.~ at
l~ast 3 or 4 atoms), cycloaliphatic. Moreover~ the
skeletal chain may be interrupted by divalent oxygen atoms
or trivalent nitrogen atoms bonded only to carbon atoms.
Rre~erably, the chain of the fluorinated aliphatic radical
does not contain more than one hetero atom (i.e., nitrogen
,
or oxygen) for every two carbon atoms in the skeletal
chain. A fully ~luorlnated yroup is pre~erred, but
hydrogen or chlorine atoms may be present as .sut3stituents
in the fluorinated aliphatic radical provided th~t not
5 more than one atom of either is present in the radical for
each carbon atom. Preferably, the fluoroaliphatic radical
is a saturated perfluoroalkyl ra~ical h~viny a skeletal
chain -that is straiyht or branchec~ and has the formula
C~F2X+l- wherein x has a value oE erc~ln I to l8.
The preferred bis~luorinclt~d aLi~hatic
sulfonyl) alkanes are those co~npound3 hclving ~he ~ormul.
R9
RfSO~- f ~SO2Rf
~1
wherein each Rf group is the same or difEerent and is a
fluorinated (preferably a highly fluorinated or
perfluorinated) alkyl group containing from 1 to 10 carbon
atoms and R9 is selected from hydrogen, halogen alkyl
groups having from 1 ~o 10 (preferably 1 to 4) carbon
atoms, alkenyl groups containing from 1 to 3 carbon atoms,
aryl groups (e.g., phenyl, naphthyl), and alkaryl groups
of up to 10 carbon atoms. The alkyl, aryl and alkaryl may
be substituted by one or more constituents selected from
halogen, highly fluorinated alkyl sulfonyl groups,
carbonyl groups, alkoxycarbonyl groups, nitro groups,
alkoxy groups, and acetoxy groups.
Fully fluorinated groups are preferred, but
hydrogen or chlorine atoms may be present as substituents
in the group provided that not more than one atom of
either is present in the radical for every two carbon
atoms. The alkyl groups generally contain not more than
10 carbon atoms and preferably they contain less than 8
carbon atoms. Most preferahly they contain up to 4 carbon
atoms.
-- I 1--
Representative examples o~ uselul
bis(perfluoroalkylsulfonyl) alkanes are:
bis(trirluoromethylsulfonyl) methane,
bis(difluorochloromethylsulfonyl) methane,
tri(trifluoromethylsulfonyl)tnethane,
bis(trifluoromethylsul fonyl)-4-t)romophenylme~hane,
bis(trifluoromethylsul follyl)-2-thienylmeth~me,
bis(trifluoromethylsulfonyl) chloromctll.me,
bis(trifluoromethylsulfollyl)l)enzyllllcthallc,
bis(trifluoromethylsulfonyl)phenylmethane,
bis(trifluoromethylsulfonyl)-l-naphthylmethane
bis(perfluorobutylsulfonyl)methane,
bis(2,2,3,3,4,4,4-heptafluorobutylsulfonyl)methane,
perfluorobutylsulfonyltrifluoromethylsulfonylmethane,
1,2,2,3,3,4,4,4-heptafluorobutyltrifluoromethylsulfonylmethane, ethyl-6,6-bis-
(perfluoromethylsulfonyl)-4-bromohexanoate, methyl-4,4-bis(perflucromethyl-
sulfonyl)-2-carbomethoxy-2-bromobutanoate, ethyl-4,4-bis(perfluoromethyl-
sulfonyl)-2-carboethoxy-2-nitrobutanoate, 1,1,3,3-tetra(trifluoromethylsulfonyl)-
propane, and l,l-bis(trifluoromethylsulfonyl)octadecane.
Representative examples of useful bis(fluorinated aliphatic sulfonyl)-
alkanes are also described in U.S. Patents 3,632,843 3,704,311; 3,701,40~;
3,776,960 and 3,794,687.
Another class of fluorinated acids useful in the present invetltion are
substantially fully fluorinated and have the formula }InXFm+n wherein X, m and n
are as described above. Specific examples of useful fluorinated acids of this
3 4 5~ 6~ Fs~ ~IPF6, AsF5 and HAsF6.
The polyvalent tin compounds useful in the catalyst system of tlle pre-
sent invention have the formula
,~
l l h f~ 3
-12-
R6
R5-Sn-R7
(~)g
whereln R5, R6, R7, R8 and 9 are each as described above.
Specific examples of polyvalent tin compound~s of this type
include diphenyl dibutyl tin, divinyl dibutyl tin, diallyl
dibutyl tin, tributyl tin ~luoride, ~riphenyl tin acetate,
dibutyl tin oxide, and bis(tributyl tin oxide)~
As has been stated, the chloroaLkylene ether
polyols of the present invention are optically clear and
substantially colorless, as i'3 demon~trated by their color
magnitude (i.e., they have a color magnitude o~ less than
10). Color magnitude represents the deviation of the
color of a given material from the color oE distilled
water when both colors are measured at about 25C. The
color of the water and of the samples is measured by a
Hunterlab Model D25-4 Color Difference ~eter available
from ~lunder-Associates Laboratory, 9529 Lee IIighway~
Fairfax, Virginia. The meter measures three parameters
which characterize the color of a sample. These para-
meters are (i) the gray component "L" of the sample;
(îi) the red~greed compnent l'a" of the sample (a plus
value indicating redness and a minus value indicating
greenness~; and (iii) the yellow-blue compnent "b" of the
sample (a plus value indicating yellowness and a minus
value indicating blueness). The color magnitude ~ E) is
calculated from the formula
E = ~ ) + (~a) + (~b)
wherein ~L, ~a and ~b respectively represent the
difference between the L~ a and b values of distille~
water and the sample being tested. Distilled water has a
color magnitude of 0 at 25Ct
Color magnitude values of less than 10 represent
optically clear and substantially colorless materials~
-13-
The color of a material having a color magnitude o~ 10 is
very light yellow and a thln film of such a material
remains optically clear. As the color magnitude increa~es
(i.e., as E increases) the color and the optical clarity
of the sample decreases. Thus, at a color maynitude oE 20
the material has light brown color and a thin film thereo~
has a hazy optical clarity. At a color magnitude o~ 50
the material has a very dark brown color and a thin Eilm
thereof is difficult to see through~
The invention is further illustra~ed by means of
~he following examples wherein the term "part~" refers ~o
parts by weight unless otherwise indicated. In the
examples the poly(alkylene ether) polyols were prepared
according to the following general procedure.
The polyethers were prepared in a glass reaction
flask which was equipped with a stirrer, thermometer, and
a dropping funnel. A dry atmosphere was maintained in the
flask during the reaction.
In each preparation the hydroxyl-containing
material (ethylene glycol, 6~.0 g, l mole) and the
catalyst system were charged to the flask and stirred and
heated to about 40~ - ~0C. The composition and quantity
of the catalyst system was varied in each reaction. The
haloalkylene oxide (epichlorohydrin or epibromohydrin) was
then slowly charged to the stirred mixture over a period
of about 3 hours. The reaction was allowed to proceed
until it was substantially complete. The temperature of
the reaction mixture was maintained between about 40 and
85C. The amount of haloalkylene oxide employed was
varied so as to control the hydroxyl-equivalent weight o
the product. Thus, for example, 938 g (lOol moles) of
epichlorohydrin were employed in order to provide a
product having a theoretical hydroxyl equivalent weight of
about 500. On the other hand 1938 g (21 moles) of
epichlo-rohydrin were employed in order to provide a
product having a theoretical hydroxyl equivalent weight of
about 1000.
.
-14-
~XAMPL.ES 1-25
Examples 1-25 represent a numL~er o~ polylchloro-
alkylene ether) polyols prepared accordiny to the above
described general procedure utilizing both prior art
catalyst systems and catalyst sys~ems o~ the invention.
The exac~ nature of the catalyst system utilized and the
results obtained are given in Table 1
The catalyst system utilized in rl~xan~le3 1-3 was
BF3; that in Example 4 was ~lSbF6~El2O; khat in ~xalnE~Ie 5
was (C~Hs)3O+p~l6- and that in Example 6 was ';bF~ can
be seen the poly(chloroalkylene ether) polyols pre~ar~!d
~rom these catalyst systems were darkly colored as is
demonstrated by their high E values (i.e., between 30 and
523~
Examples 7-9 demonstrate the effect of the
individual components of the catalyst system oE the
present invention upon the poly(chloroalkylene ether)
polyols produced~ Thus, in Example 7 the catalyst system
was a polyvalent tin compound of the formula
R6
R5-Sr,_R7
(~8)~
(i-e-~ (C6H5)2Sn(C4H9)2)- As can be seen from Example 7
there was no reaction even after 5 hours of mixing when
the diphenyl dibutyl tin compound was used as the catalyst
system. When the catalyst system was the sulfonyl alkane
compound (Examples 8 and 9) darker products than those of
the invention were obtained as is shown by their color
magnitude.
Examples 10-12 demonstarate the criticality of
the molar ratio of the HmXFm_n fluorinated acid to the tin
compound in the catalyst composition of the invention.
Thus in Examples 10 and 11 the ratio was 1:1 and 1.1:1.
In each case the resulting product had a very daL^k brown
~hL~ 3
-15-
(i.e., ~E of 53.1 and 52.9 respectively). However, in
Example 12 the molar ratio was 1.13:1 and the resulting
product was optically clear and substantially colorles~
(i.e., a color magnitude of 2.1).
Examples 12-24 demonstrate the present
invention. In each o~ these examples an optically clear
and substantially colorless poly(chloroalkylene ~ther)
polyol was obtained, This is demonstrated by the lo~l~E
values obtained (i.e., QE less than about 5). ~xamples
12-16 show the effect oE varying the molar ratio o the
~mXFm+n fluorinated acid to the polyvalent tin compound.
Examples 17-20 show the use of the bis(fluorinated
aliphatic sulfonyl)alkanes and the use of varying ratios
of this acid to the tin compound in the catalyst system~
Examples 21-24 show the use of differing tin compounds in
the catalyst system. Example 25 shows that highly
halogenated alkylene oxides (e.g., l,l,l-trichlorobutylene
oxide) can also be used in the present invention~
--16--
~D ~O ~O ~D Ln ~ ~ Ln Ln Ln Ln Ln
Ln ~ ~ Ln ~ ~ Ln ~1
o ~ ~i ~ ~i ~, o ~
a Ln Ln ~r In ~ ~ ~ ~ Ln Ln O
~r a) o Cl~ O O o o o ,,~
O O Ln o ~ ol ~ ~ o o o C: o
3 ~ a~ ~ r ~
~ ~ ~ ~r ~) ~ ~ ~ ~ 3 ~ ~I r` ~ n
.~ ~b
n O ~ LOn c~ o ~ O O O
O _ ~ o ~
~ ~ oooooooo 7~
' ~ ,~ ~ ~-1 ~ o Ln Ln ~ ~ ~ o
. o o o o o o o o o o o o o o
~ o ~ ~ ~ 3 ~ ~ o
. N N N N N N '~
. V V ~ V~ V~ V~
m ~ N ~1 N N N
V~' V ~ V V~
~ ~ ~ æ ~ Ln N N ~ 2~ N 5~
~¢ ~ ~ ~~ N ~ X ~C 5 ~::
. ~ m ~ ~
~i ~ ~ ~ ~ Ln ~D ~` CO a~ ~ ~ ~ ~ ~ I
17
r ~D o
r~ o
;~ ~ ~ r ~ r~
~; O ~ ~ G~ ~r r~
o ~ ~Y o co ~ o a
!~ ~ ~` r~ rrr
~ ~ O O ~ O ~
~ ~ a~
C ~ ~r ~ ~ ~ ~r ~r ~r ~r ~r ~ ~5
~ ~
~:
~r a~ r ~ SJ
~O N 1~ ~r ~r It') ~ ~ --1 0
o O O O O ~ ~ ~
OOOOOOOOC3LnO--1
~; ~ ~ 3 o
O O O O O O O O O O O
~ ~ ~ a~
p~ o ~ ~ ~ ~
~ ~ ~ o~
~ ~ ~ O ~ o o O ~
5Q
-- ~
~r m ~ Cr ~r ~r
u v ~ y
~q ~ O
!~ ~ m c
u~ t~ t~ t~ t~ t~ t~ t~ t~ t~ t~ t~
E~ _ ~
~ ~ .~
~ ~ ? o ~ h
t~ ~ t~ ~ ty ~ O
O O
~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
~ .;~ ~ I
cn n~
` r
u~ tE4 t~ t4 t~ tE4 t~ t~ ~ a ~ ~
~3 I~7 ~ r~ co ~ c: ~ ~ ~ ~r ~ _ Q
_ _
-18-
EXA~PLES 26-27
A series of hydroxyl-terminated poly(halo-
alkylene ethers) were prepared as described in the general
procedure. The resultant polyethers were tested for
initial color magnitude then subjected to heat (80C~ for
14 hours after which time the polyethers were tested Eor
final color magnitude. Example 26 was per-formed usiny a
sample from the polyol prepared in Example 13 oE Table 1.
Example 27 was per~ormed using a ~90 hydroxyl equivalent
]0 weight polyether prepared according to the general
procedure but employing (C2H5)3O~PF6~ ~0.~% by weight o~
the combîned weight of the ethylene glycol and the
epichlorohydrin) as the catalyst system.
TABLE 2
Example EI ~EF
2~ 1.51 1.56
27 18.55 30.41
~EI is the initial color of the polyol in the test. AEF
is the color of the polyol after heat aging at 80C for a
14 hour period9 The behavior of Example 26 is
characteristic of all the polyols of the invention. As
can be seen, poly(chloroalkylene ether)polyols of the
invention exhibit essentially no change in color magnitude
while prior art poly(chloroalkylene ether)polyols darken
drama~ically in color.
EXAMPLES_28-34
A series of polyurethanes were made using
various poly(chloroalkylene ether)polyols, and a poly-
functional polyisocyanate. The polyols were prepared as
described in the general procedure. The polyfunctional
isocyanate was "Mondur MRS'~(a polymethylene polyphenyl
isocyanate having an average oE about 2.6 isocyanate
groups per ~olecule and being available Erom Mobay
Company)~
r
-19-
The polyurethanes were prepared by combining the
ingredients in a suitable reaction vessel and stir~ing
them for 1-2 minutes at a temperature of about 25C~ A
moisture free atmosphere was maintained in the reaction
vessel. These was no catalyst added to promote the
reaction.
Examples 28 and 29 utilized poly(chloroalkylene
ether)polyols accordiny to the invention, These polyol3
were prepared using the same cataly~t sy3tem ancJ amount~
thereof as are set forth in Example 15. The polyol
employed in Example 28 had a theoretical hydroxyl~
equivalent weight of 325 while the polyether employed in
Example 29 had a theoretical hydroxyl equivalent weight of
500.
Examples 30-34 utilized poly(chloroalkylene
ether)polyols prepared from prior art catalyst systems.
The polyol employed in Example 30 had a theoretical
hydroxyl equivalent weight of 1000 and was prepared
utilizing BF3 (0.3~ by weight of the combined weight of
the epichlorohydrin and the ethylene glycol~ as the
catalyst system. ThP polyols employed in Examples 31 and
32 had theoretical hydroxyl equivalent weights of 500 and
325 respectively and were prepared utilizing ~C2Hs)3O+PF6-
(0.2% by weight of the epichlorohydrin and the ethylene
glycol) as the catalyst system. The polyGls employed in
Examples 33 and 34 had theoretical hydroxyl equivalent
weights of 500 and 325 respectively and were prepared with
HSbF6-6H2O (0.1% by weight of the combined weight of the
epichlorohydrin and the ethylene glycol) as the catalyst
system.
The results of the preparations are given in
Table 3. As can be seen the polyurethanes of Examples ~8
and 29 ~prepared according to the invention) gelled
quickly while the polyurethanes of Examples 30-34
~prepared according to the prior art) did not gell even
after ~4 hours. Moreoever, the polyurethanes of Examples
28-29 cured within 24 hours while those of Examples 30-34
4~
-20-
d.id not cure even after 3 days.
TABLE 3
Polyurethane Viscosity (cp~)
Initial Final
Example NCO/OH (Time=0 hours) (Time=24 hour~)
28 1.2:1 4800 Gelled wlthin 15*
minute~
29 1.2:1 220U Gel.led within 15*
minutes
1.2:1 5900 24000
31 1.2:1 5~00 16000
32 1.2:1 2300 5400
33 1.2:1 4~00 15000
34 1~2:1 2200 27000
*Gellation occurs when the viscosity >1,000,000 cps.
EXAMPLES 35--40
A series of hydroxyl-terminated poly(chloro-
alkylene ethers) according to the invention were prepar~d
according to the general procedure except that various
hydroxyl containing materials were substituted for
ethylene glycole In each of these examples the catalyst
system comprised 0.1% HSbF6-6H20 and 0.224~ diphenyl
dibutyl tin (both percentages being percentage~s by weight
of the combined weight of the hydroxyl material and the
epichlorohydrin~. The resulting polyols were then tested
for percent conversion, hydroxyl equivalent weight and
color magnitude. Th exact ingredients used to prepare
the polyols, the amounts of each and the results obtained
are reported in Table 4.
-21-
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-22-
EXAMPLE 41
A hydroxyl-terminated po1y(bromoalkylene ether)
according to the invention was prepared. A mixture of
cyclohexanedimethanol (72 g, MW 144, 0.5 mol~s) and
methylene chloride (500 ml) was heated to ~0C and the
catalyst system (48% aqueous fluoboric acid arld 1.8 g of
diphenyl dibutyl tine) 3.~ g was added. Epibromohydrin
(purified by distillation, 52% g) was then added slow1y
over a period of one hour into the mixture ~nd the
reaction temperature was maintained at ~0-45C. The
mixture was allowed to stir at ~0C for 16 hour~ after
which 58% ammonium hydroxide was added and stirred until
the mixture reached a pE~=7. Anhydrous magnesium sulfate
and Celite~ were added slowly, stirred and filtered. The
solvent and residual epibromohydrin were removed under
vacuum~ A 96% yield of a yellowish polyepibromohydrin was
obtained. It had a hydroxyl equivalent weight of 358, a
weight average molecular weight of 1023, a number average
molecular weight of 817 ! and a bromine content of 46~7%.
EXAMPLE 42
A hydroxyl terminated poly(chloroalkylene ether)
according to the invention was prepared. A mixture of
cyclohexane dimethanol (36 g, MW 144, 0.25 moles) and the
catalyst system (0.31 g of 48% aqueous hydrofluoric acid
and 0.17 g of diphenyl dibutyl tin) was heated to 60-65C.
Epichlorohydrin (214 g, 2.31 moles) was added slowly to
the mixture while maintaining the same temperature. The
reaction mixture was allowed to stir for an additional 16
hours. Vacuum distillation provided a yield of 72~ of
colorless and slightly cloudy poly~chloroalkylene ether)
according to the invention, The product had a hydroxyl
equivalent weight of 332~ a weight average molecular
weight of 838, and a color magnitude of 1.69.
The yield of the chloroalkylene ether may be
improved to 97.3~ by utilizing a catalyst system of 0.75 g
of 48% aqueous hydrofluoric acid and 0.5 g of diphenyl
-23-
dibutyl tin. The product obtained from this reaction has
a hydroxyl equivalent weight of ~07.
