Note: Descriptions are shown in the official language in which they were submitted.
3~
POLYMERS CONTAINING 225-OXOLANYLENE SEGMENTS
`~ -
Thls inventlon relates to polymers contalnlng
2,5-oxolanylene segments. More partlcularly it relates to
polymers contalnlng recurrlng 2,5-oxolanylene tor oxolane)
unlts of the rormula
. ~ C C ~ _ _
~ CH
: Al R2
wherein at least 60% of said unlts are jolned directly to
one another so as to provide segments contalning at least
slx of sald units and whereln Rl, R2, R3 and R4 are
lndlvldually hydrogen or alkyl groups containlng up to
8 carbon atoms each. ~he inventlon also relates to
~; methods of preparing the polymers and to articles whlch
employ them.
,:
The polymers of the present lnvention are highly
~ active ln altering the surface propertles of substrates,
;,~; for example, relatlve to adheslon and hydrophoblclty, and
~ are capable of forming compatible~(i.e. homogeneous) blends
r ~ ~ 20 wlth high and low moleoular weight thermoplastic and
thermosettlng resins and polymers. Additionally the
;
polymers o~ this invention can be used to prepare graft
copolymers having deslrable physical characteristlcsO
~- Thus, substrates coated with polymers Or the
invention exhlblt lmproved adhesion to varlous surfaces~
~ j For example, pressure-sensitlve adhesives exhlbit lmproved
'.~ adhesion to polyester and polyolefin films coated with
poly-2,5-oxolane-contalning polymers.
, . .
,
~:
*~
Additlonally, normally hydrophobic surfaces can
be rendered hy~rophilic when coated wlth polymers of the
invention. This ls of partlcular use when the polymers are
employed on polyester films (e.g. polyethylene terephthalate,
copolymers of terephthalic acld and lsophthalic acid with
ethylene glycol etc.) and polyolefin fllms (e.g., poly-
propylene films). Such fllms are not readily receptlve to
water-based lnks and dyes unless first sub~ected to
relatlvely complicated treatments (e.g., using corona
dlscharge techniques, etc.). It has now been found that
the same r-esult can be obtalned by slmply treatlng such
normally hydrophoblc films wlth the polymers of the invention.
The abllity of the polymers to form compatible
blends with a number of other polymers and resins is both
unusual and valuable. While certain polymers are known to
be compatible with other polymers and resins, this char-
acterlstic is very unusual. Thus the opportunlty for
blending polymers to obtain mixtures having desired properties
is normally very limited.
The broad compatlbility of the poly-2,5-oxolany-
lene polymers of the present invention is o~ great value.
Homogeneous blends of the polymers with other polymers
result ln products having prope~ties different from either
component alone, e.g. such blends have a single glass
transition temperature. Thus a thermoplastic palymer with
which the polymers of the inventlon form a homogeneous
blend (such as polyvinyl chloride, chlorlnated polyvinyl
chloride and polymethylmethacrylate) can be permanently
plasticized by the addition of an amount o~ a polymer of
the invention. Additionally, the brittleness and~or lack
--2--
of adhesion to substrates frequently encountered with
thermosetting reslns (such as epoxy resins) can often be
overcome by blendlng an amount of a polymer Or the present
inventlon thereln prlor to curlng. The polymers of the
lnventlon are compatible wlth such other polymers ln all
proportlons. Normally, however, the compatible blends
contain from about 1 to 90 weight percent of the polymers
of the invention and from 99 to 10 welght percent of the
said other polymers.
The polymers of the present lnvention may be
homopoly-2,5-oxolanylenes or they may be copolymers con-
talning segments of 2,5-oxolanylene unlts together with
substantial amounts of other unlts. Preferably the
polymers have molecular weights ranging ~rom about 420
to 1,500,000 tordinarily correspondlng to a degree of
polymerizatlon of about 6-20,000 with respect to all
recurrlng units). Preferably also the polymers contain
at least about 10 percent by weight of units of type I.
:
The copolymers may be block or graft copolymers~ and the
segments of units I preferably appear therein in the main
polymer backbones. Both the homopolymers and the copolymers
- normally contain small amounts Or defect structures due to
the nature of the process for their preparation. In the
; `~ homopolymers, units containing such defect structures are
. 25 limited to less than about 15 percent of the weight of the
.j
polymer, an amount insufficlent to have any substantial
, ~ effect on the properties of the homopolymer. As wlll be
~ explained hereinafter, such defect structures include the
,~ addition products of fragments of nucleophiles or electro-
,~ 30 philes used as ring expansion inltiators, solvent fragments~
` etc.
-3-
,
:
wherein Rl, R2, R and R4 are, individually, hydrogen or alkyl groups con-
taining up to 8 carbon atoms each, provided that the totality of such
segments in the polymer contain from about 20 to 100 mole percent of type
I units of which at least 60 percent are joined directly to one another
so as to provide uninterrupted chains of at least 6 such units, 0 to 80
mole percent of type II units and 0 to 20 mole percent of type III units.
In another aspect, the invention provides a method of preparing
a polymer containing recurring units of the formula
_
/ \ / R3
H-C - C-H
l R4
wherein at least 60 percent of said units are joined directly to the other
so as to provide segments consisting of at least six of said units; and
wherein Rl, R2, R3 and R4 are, individually, hydrogen or alkyl groups
containing up to 8 carbon atoms each which comprises
(i) substantially epoxidizing a precursor having the repeating
:.~ unit
:~ H
.-- C C--C C--
R R2 R3 14
and
(ii) treating the resultant epoxidi~ed precursor in the presence
of a minor amount of an initiator selected from strong nucleophiles and
strong electrophiles to initiate polymerization of oxirane rings by a
ring opening mechanism.
The invention also provides a compatihle blend of the polymer
-4a-
~3'
~6~
Other structures which can be present in the polymers of the inven-
tion include units resulting from the incomplete reaction or non-reaction of
units of the poly-1,4-dienes from which the present polymers are prepared
~as will be explained hereinafter), i.e. units of the types
-1-1 /\ 1-1
C - C - C - C~
and
C - C - C C ~ III
R R
wherein Rl, R2, R3 and R4 are as previously defined.
Thus, the present invention preferably also provides a polymer
containing segments consisting essentially of lmits of the formulae
R ~ / \ C/ ~ ~__
H-C - C-H
l R4
H / \ H
- C - C - C C - ~ II
2 R3 R4
- and
H H
- - C C _ C - C - -------- III
ll l2 R3 l4
~' 13
3~
defined above and a second polymer selected from polymethylmethacrylate,
polyvinyl chloride, chlorinated polyvinyl chloride, epoxy resins and poly-
esters.
The polymers of the invention are thus prepared in two steps from
a polymer precursor which contains one or more A segments having a perfectly
recurring structure of type III units
R R R R Segment A
where x is the number of times that each unit III recurs in segment A. Thus,
~" a single A segment continues so long as the sequence of recurring main chain
olefin groups, each separated from the next by two main chain carbon atoms,
continues. The termini of each segment A are either one or both polymer
chain ends or any anomalous (different) group
~; '
;~:
~ '
:~
"::
,, -
'Y,~ ~
: .
~:
, X~
.,
I .
:
`~ -4~-
.,
;~
,~
,~ ~
which intervenes between these segments. Such anomalous
groups wou~d, for example, lnclude 1,2- or 3,4-diene
addition products
HCR4
l~3
- CH
~1 ~2
lncorporated comonomer units, e.g. a single styrene unit or
a recurrlng segment or block of styrene units. It ls
important that these lntervening or anomalous groups be of
such a character that they do not interfere wlth the sub-
sequent epoxldation reaction, which ls discussed below.
In any polymer used as a precursor ln the
present process, the tYpa III unlts must amount to not
less than 80 percent o~ all dlene units thereln (i.e. a
minor amount, not more than 20 percent may be diene unlts
containing unsaturation ln the side chains, such as 1,2-
and 3,4-butadiene units)O Also at least about 50 percent
of all type III units ln the precursor polymer must be
present ln A segments which contain at least 10 units.
The precursor polymers may range in degree of polymeriza-
tion from about 6 to 20,000 with respect to units of
type III. The range of from about 100 to 4,000 is most
preferred, however, since the polymers of the invention
prepared from them generally have the best balance of
physical properties (eOgO, acceptable ~ensile strength
combined with acceptable handling characteristics).
Sultable precursor polymers can be provided ln
various ways. For example, natural rubber and gutta percha
constitute such precursor polymers in which essentially the
entire high molecular welght polymer ls constituted of
one such segment (1,4-poly-cls~isoPrene and 1,4-polY-
trans-isoprene, respectively). They may also be provided
using synthetic routes well known to those skilled in the
art. Thus, 1,3-diene monomers may be anlonically poly-
merized (e.g., using butyl lithlum as initlator in a non-
polar solvent such as cyolohexane) to provide a suitable
precursor polymer in which 1,4-addition predominates over
1,2-addition to yield segments having the requislte
structure described above, whlch recur within the polymer
backbone. In thls case, however, 1,2-addition usually
occurs to the extent of 5~20 percent to give rise to
anomalous lntervening groups separating the recurring A
segments. Zlegler polymerization of 1,3-dienes, in which
one or more transitlon metal compounds ls used as initiator,
is a highly preferred method of providing precursor
polymers because the grèat predominance of 1,4 addition
gives polymers typically containlng 95-99 welght percent
;~ of A segments. Another way of providing sultable precursor
polymers contalning a large proportlon of A segments ls by
the use of specified transition metal lnitiators to
polymerize cyclobutene, as de~cribed by G. Natta et al,
MakromolO Chem. 91, pps. 87-106 ~1966).
When the polyme~s are prepared from ~opoly-1~4-
dienes, the units resulting from the other comonomers
thereof will be presentO Such units do not enter lnto the
reaction by which the 2,5-oxolanylene units (I) are formed
and ordlnarily come irlto the copolymers of the present
in-vention from the precursors unchanged. Such units lnclude
for example the type
-6-
~,
"
R5
--C C r--- IV
R6
wherein R5 is hydrogen or methyl and R6 is phenyl, cyano
or -CooCH3. These would be present as a result of the
lnclusion of the anionically polymerizable olefins as
styrene, ~-methylstyrene, acrylonitrile, methacrylo-
nitrile, methylacrylate and/or methylmethacrylate as
comonomers ln the precursor dienes.
Suitable precursor graft and block polymers can
be prepared by techniques known to the art. For example,
the graft polymers can be prepared by the free radical
polymerization of ethylenically unsaturated monomers such
as methylmethacrylate, methylacrylate or styrene with the
appropriate polymeric precursor wlth subsequent conversion
of the olefin group to the oxolanylene structure. Block
polymers suitable for use as precursor polymers of the
lnvention may be prepared by, for example, the techniques
descrlbed in D.C. Allport and W.H. Janes, "Block Copolymers",
Chapters 3 & 4, Halstead Press, 1973, and in M. Sr~warc,
"Carbanions, Living Polymers and Electron Transfer Process",
Interscience Publishers, 1968. Representative commerclally
available block copolymers suitable for use in preparing
polymers of the lnventlon include polystyrene-polybutadienP-
polystyrene block copolymers, polystyrene-polyisoprene-
polystryene block copolymers.
It will be appreciated by those skilled in the art
that A segments, when they recur within the polymer molecule,
will normally be present in a relatively wide distribution
of lengths. However, knowledge of the number of III units
relative to the number and type of anomalous groups or
segments whlch separate A segments makes lt possible to
calculate the median A segment length x (using standard
probabllity theory). The term, median segment length,
as used herein connotes that largest value of x, i.e. the
segment length, wherein half of all the mass of the units
Or a particular type recurring in the polymer (especially
type I units) occur in segment lengths equal to or
greater than xO
The epoxidation of the polymer precursor is
normally performed so as to convert substantially all main
chain olefin groups into oxlrane groups. When such con-
verslon is quantitative, all III units are converted to
II type units to form B segments having a perfectly
recurring structure of such units
O --
- CH - C - C - CH - - Segment B
l ~2 l3 l4
x
which have the same median segment length x as the A segments
of the precursor polymer. To the extent that epoxldation
falls short of con~erting 100 percent of the III units,
commensurate reductlon in the median B segment length
occurs. In any event, it is critical that the epoxidized
polymeric lntermediates used to prepare the polymers of
; this in~ention also have the median B segment length x of
at least 10.
The epoxidlzation is generally carried out by
~he reac~ion of the precursor with a peracid (e ag ~ ~
peracetic acid). Typically, the reaction ls carried out
':
f3~
at about 30C. or less and at atmospheric pressure using
stoichlometric amounts Or the reactants. After the
reactlon has been completed, the polymer is recovered
from the reaction mixture by, for example, precipitation,
and the precipltate is purified and dried.
In the ring expansion step of the process, an
appreciable fraction of the oxirane groups ln the B
segments of the epoxidlzed polymer is converted to type
I units. It is a particularly significant aspect of the
inventlon that polymers containing B segments having the
~ requisite structural features discussed previously can be
- made to undergo an lntramolecular (more specifically --
an lntrasegmental) chain reaction in which a large
fraction of the oxirane groups within the B segments are
converted to ring-expanded, recurring ?,5-oxolanylene units.
The hypothesized course of the reaction is as follows
(shown separately for nucleophllic and electrophilic
initlation).
.~ ~
,.~
.
,.:
~'
_9_
i~
'~
~,~
''''~ '
344
Nucleophlllc Initlation
--c c fc c--~c--c=c--c~
Epoxidatlon
o ~I o
-c c~ `c--c~c--c~--b--c~
Initlatlon by ~
Nucleophlle (Q ~ )
--C--C--C--C~ C/\C--
Ring Expansion
--c--c--c~b ~I c--c~--c ~c~ ~c--c~n l
c c ~I
C - QC - C/ \C - C/ \C C ~ C - C/-\C - ~
~ `lcc-l L
¦ n-2
Termination by trans~er ~
~: to solvent or Catalyst ~H ~ )
.
0\ ~ ~ /O\ /OH
C C C G - C C- - C
: I I I I
~ C C C - C n-l
:
10-
.
3~
Electrophilic Initiation
C ~C--C C ~C C=C--C~
Epoxidation
/o\ ~ /o\
C - C--C C~C---C--C--C
Initiation by
- Elec~rophile (Z ~ )
H
C C/~\C~C--C--\C- C~
~ I
Rlng Expan~lon
--c I--c~ b--c~ cA
C C
C CH C/ \C _ ci \~ - C/- ~ C G b_ c~
C C C ¦ n-2
Terminatlon by transfer
to Solvent or Water (W)
--C--C--C/ ~C ~C/ \C~ C /
C - C Lc - CJ n-l
~'
,:;
-11-
,~
3~
Thus it appears that the lnitiatlon step proceeds
via the cleavage of a randomly situated oxirane ring
located within a B segment to generate a reactlve lonlc
intermedlate The latter then reacts wlth an ad~acent
oxirane ring to start an lntramolecular chain propagatlon
reaction in which an uninterrupted sequence of ad~acent
oxirane groups is rapldly converted to an uninterrupted
sequence of 2,5-oxolanylene groups ~oined one to the
other. Thls chaln propagatlon (or ring expansion) reaction
proceeds wlthin a slngle B segment of the polymer molecule
until a terminus group of that segment is encountered and
: .
chain termination occurs. It is believed that this
` termination generally entails a chain transfer reaction
with either an initiator or a solvent molecule to append a
i~ 15 new termlnal group, e.g. a hydroxyl or methoxyl group, and
generate a new initiating lonj e.g. a proton in the case
of an electrophillcally initlated ring expanslon reactlon,
or a hydroxide or methoxide ion in the case of a nucleo-
phlllcally lnitlated ring expansion reactlon. The thus
~enera~ed lon is then free to lnitiate a similar ring
,: ~
expansion reaction on another oxlrane segment situated
either on the same polymer backbone or on the polymer
backbone of a different moleculeO
It follows that:
(1) The requislte structural features set forth for
polymers containing B segments must be met in
:~,
;~ order to support the formation of 2,5-oxolanylene
c:
~; units in the necessary numbers and arrays (i e.
~;; segments containing consecutive oxolanylene
:j ~
~ 30 groups).
,',"'
-12-
~'~
'~
:
(2) The longer a particular B segment, the more
likely lt ls to undergo the ring expansion
reaction. Even at relatively low oxirane
conversions (e.g., 20 percent), relatively
long segments of recurring 2,5-oxolanylene
groups are produced.
(3) The median segment length of recurring 2~5-
oxolanylene groups ls a function both of the
weight median length of the B segment from
which they were derived and the overall degree
of conversion of oxlrane grouPS at the point
at whlch the ring expansion reaction is
terminated.
(4) The median length of the segments produced
toward the end of the ring expansion reaction
is smaller than that of the segments produced
near the beglnning thereof.
(5) Polymers in which the epoxldized B segments
constitute at least 97 percent of the weight
~0 of the total polymer chain (derlvable from
natural rubber, gutta percha and polymeric
dienes made with Ziegler~type initiators) can
be made to yield ring-expanded products in
which 2~5-oxolanylene units recur in extremely
long segmentsj e.g. weight average segment
lengths of 100 or more.
The ring expanslon reaction is carried out in
the presence of an lnitiator selected from reagents which
are known to lnitiate homopolymeri~ation of oxiranes by a
ring opening mechanism, but whlch preferably do not undergo
-13-
3~
addition reactions with the oxirane groups. Partlcularly
useful initlators are strong nucleophiles (tertiary amines
such as trialkylamines, e.g. trlethylamlne, and alkali
metal and quaternary ammonium hydroxides~ especially the
preferred tetraalkylammonlum hydroxldes, e.g. tetrabutyl
ammonlum hydroxide) and strong electrophiles (Br~nsted and
Lewis acids such as phosphoric acid, hydrochloric acid,
SbF5, AsF5 and BF3 and other electrophiles including
bis~trifluoromethylsulfonyl)bromomethane, the diethYl ether
complexes of Lewis acids such as boron trifluoride
diethyletherate, and organometallic initiators such as
Al(C2H5)3 H20. A minor amount of initlator (e.g., from
about 0.1 to 10 mole percent, based on the amount of oxirane
present) is used.
Normally the rlng expansion is carried out in a
polar solvent such as 1,4-dloxane or a mixture of dioxane
and methanol at from about -50 to 150C. and takes from
about one to 16 hoursO The severity of the conditions
(iOeO time and temperature) are directly relatable to the
activlty of the initiatorO It is known that electrophilic
initiators are generally more reactive with these types of
oxiranes and thus milder reaction conditions (e.gO 1 to 8
hours at -50 to +30~Co) can be employed when an initiator
such as SbF5 is usedO Nucleophilic initiators generally
requlre more stringent condltions, e.gO 2 to 16 hours at
50 to 150Co The reactlon may be terminated at any time
,
prior to complete conversion o~ the oxirane units to
oxolanylene unitsO Alternatively, the ring expansion can
.-
~ be carried out in the solid state by adding the inltiator
;'~
,:~
-14-
3~
to the epoxldlzed precursor, coating the combination onto
a substrate, drying and heating at, for example, 100C.
The resultant polymer ls then recovered by
precipitatlon from water and may be ~urther purified by
redissolving and repreclpitating.
As prepared, the polymers of the inventlon are
water-insoluble (i.e. are less than about 2 percent
soluble ln water at 25C.) and cannot be spontaneously
dispersed in water. However, such polymers may be made
water-dlsperslble and/or water~soluble by means of post-
reactlons (reactions by which certaln structures are
appended to already formed polymers o~ the lnvention).
Such structures are convenlently added by the ionic
opening of oxirane rings remaining ln the polymer (in
units of type II above) by reactlon wlth elther an
electrophilic or a nucleophillc ring opening reagent to
form units of the formula
H OH Y H
ll ¦2 i3 1 V
where Y ls the radical corresponding to the ring opening
reagent having the structure Y-M wherein M is hydrogen or~
an alkall metal. Common Y radlcals are, for example,
- hydroxyl, amino, sulfo, alkoxyg aroxy, thiol, carboxylate
:~ 25 ester and alkylthla whereln the indivldual aliphatic groups
(eOgO, in the amino, alkoxy, carboxylate ester and
- alkylthia groups) contain no~ more than 8 carbon atoms and
,
; the individual aryl groups (in the aroxy) contain not more
t'nan 6 carbon atomsO 15-
'~
The followlng are 80me of the preferred sub-
classes of the polymers of the lnventlon:
Those polymers consisting essentially of from
about 10 to 100 percent Or units o~ type I, from about 0
to 90 percent of units of type II and from about 0 to 10
percent of unlts of type III.
Those polymers which conslst essentiallY f
from about 20 to 100 mole percent of segments or blocks
of units Or type I and from about 0 to 80 mole percent of
~; 10 segments of units of type II.
Homopolymers in which Rl, R2, R3 and R4 are each
hydrogen or in whlch R~, R2 and R4 are hydrogen and R3 is
an alkyl radical, most preferably methyl.
Preferably the number average molecular weight
of the polymers of the invention is at least about 420 and
- not more than about 200,000. Normally and preferably also,
the polymers of the invention are substantially completely
- soluble ln chloroform at 20C, and to the extent of at
:
least 10 parts by weight of polymer in 90 parts by weight
~-- 20 of chloroform.
The structure o~ the oxolanylene-containing
polymers of the invention can be demonstrated by proton
nuclear magnetic resonance (NMR). For example, the
analysi of a 2,5-oxolanylene polymer derived from cis-1,4-
polybutadiene was run in deuterochloroform as the solvent
and all chemlcal shifts (i.e. absorptlon peaks~ were
reported in parts per million ~ppm) from tetramethyl-
silaneO The peak assignments were as follows:
-16-
':
A. The epoxide precursor
_ _ 3.0 ppm ("cls11)
/ \ ~ 2.8 ppm ("trans")
-CH2 - CH - Cl-l- CH2~ _
l.7 ppm
B. The oxolanylene product
/ \ ~ 3.9 ppm
. - CH CH -
: H2C - CH ~
1.7 ppm
CO Typlcal "other" functional groups
CH3 ~ - - 3.4 ppm
0 OH
I
. ~ CH2 CH CH -
~; 15 ~ - - 3.4 Ppm
'~ 3.4 ppm
-
The "other" functional groups in C are typicaliy initiatlon
and terminatlon sites of a sequence of 2,5-oxolanylene
units. They may result from transfer to the catalyst, or
reaction solvent, etcO The assignments set forth in C are
for groups whlch result when an epoxldlzed polybutadiene
is ring expanded in the presence of tetramethyl ammonium
methoxlde in a solvent blend of methanol and dloxane
(90 p~rcent).
Transition temperature measurements (particularlY
the Tm, the crystalline melting temperature) at various
stages of conversion of the epoxidized polymers to the
polymers of the invention demonstrate that segmented
copolymers having sequences of I and II type unlts are
belng formedO These segmented copolymers provide a useful
. -17-
method of varying the physical propertles of t~e polymers
of the lnvention (since lt ls possible to stop the con-
version from the tough, strong, epoxidized polymer to the
elasto~eric, compatible oxolanylene polymer at any point).
The formatlon of segmented polymers also verlfies the chain
reactlon mechanism proposed for the ~ormation of the
oxolanylene segments. Thus, a polymer consisting of type
II units derived from poly-1,4-butadiene has a crystalline
melting point at 80C. This crystalllne transitlon is
present after 70 percent of the II units have been con-
verted to I units. It is well known that a crystalline
transition in a Polymer is only present when the polymer
units are present in an uninterrupted and regular sequence.
Therefore the remaining 30 percent of type II units must
` 15 be present in sequences. This then dlctates that the
type I units formed are also in sequences.
- The following examples further illustrate the
present invention.
"`'
-18
Example 1
A polymer o~ the invention prepared from cls-
1,4-polyisoprene.
The following two solutions were prePared:
Solution A
cls-1,4-polyisoprene100 grams
(number average molecular
weight, Mn= 100,000)
dichloromethane 2000 ml.
Solution B
.~
' peracetlc acid solution* 353 grams
sodium acetate (buffering
agent)24 grams
:
*40% peracetic acld, 40% acetlc acid,
13% water, 5~ hydrogen peroxide and
2% sulfuric acid
Solution B was slowly added to solution A from
~ a dropping funnel over a two hour period~ the temperature
:
;~ o~ the mixture being maintained below 5C. The mlxture
was then reacted for an~additional 30 minutes while
; malntalning a temperature less than 5C. The resultlng
epoxidized polymer was precipitated in methyl alcohol and
washed four times w1th oopious quantities of methyl
; : alcoholO The polymer was 98 percent epoxldized.
The following lngredients were charged to a
reaction vessel in a nitrogen atmosphere:
epoxidized polyisoprene (from above) 2 grams
dimethyl sulfoxide
(reaction solvent) 40 grams
orthophosphoric acid
(catalyst or initiator) 0.12 gram
--19--
The reaction mlxture was malntained under nltrogen for
16 hours at 100C. wlth agltation. The resultant 2,5-
oxolanylene polymer o~ the invention was then precipitated
and washed with water.
In a slmilar run 2 grams of epoxidlzed poly-
isoprene, 40 grams of 90/lO dioxane/water solvent and
0.2 gram of (CF3S02)2CHBr catalyst or initlator were
reacted under the same conditions. Analysls o~ the
polymer indlcated that about 75 mole percent of the
oxirane groups had been converted to 2,5-oxolanylene unlts
and that at least 60 percent of these units were ~oined one
.
to the other ln segments conslsting of at least 6;of said
units.
:'
Example 2
A polymer of the invention prepared from cis-l,
4-polybutadiene.
;
The following two solutions were prepared:
Solution A
cis-1,4-polybutadiene150 grams
(M = 9g2i analysis 98%
ma~n chaln olefln units of
type III, 2% vinyl units
resulting from 1,2-
butadiene addition)
methylene chloride3000 ml.
Solution B
peracetlc acid solution 530 grams
(as described in Example l)
sodium acetate 36.8 grams
(buffering agent)
-20-
:
,.
Solution B was slowly added to solutlon A from
a dropping funnel over a 40 minute period, th~ temPerature
of the mlxture belng malntained below 30C. The mixture
was t~en reacted ~or an addltlonal 3-12 hours whlle
malntalnlng a temperature o~ less than 25C. The resultlng
epoxldized polymer was preclpitated ln methyl alcohol,
redlsso~ved in p-dioxane and repreclpitated in distllled
water~
The polymer was 98 percent epoxldized.
The followlng lngredlents were utilized in
converting the epoxldlzed polymer to a polymer of the
inventlon:
~; polybutadlene 20 grams
(98% epoxidlzed)
dioxane (reaction solvent) 340 grams
~` distilled water 40 grams
(CF S0 ) CHBr (catalyst- 2 grams
50%3so~u~ion by welght
in dioxane)
The ca~alyst was 510wly added to the other
ingredients with vlgorous agitatlon and the mixture was
agitated and reacted at 25C. for six hours. The catalyst
was neutralized with tetraethYlammonium hydroxlde, and the
2,5-oxolanylene polymer was recovered by precipitating and
2~ washing the polymer with distilled water.
Analysis of the polymer indicated that about 85
mole percent of the oxirane groups had been converted to
2,5-oxolanylene units and tha~ at leas~ 60 percent of these
units were Jolned one to the other in segments conslsting
of at least 6 of said units.
-21-
Example 3
A polymer of the lnventlon conslsting essentlall~
of units of types I and II.
Epoxldized cls-1,4-polybutadlene was prepared as
described ln Example 2. A solutlon of 30 grams of the
polybutadlene in 730 grams of dioxane was warmed to 75C.,
and 111 grams of a 10 percent by weight s~lutlon of
tetrabutylammonium hydroxide in methanol was added. The
mlxture was reacted ln an inert atmosphere at 75C.
Individual samples were removed from the reactlon mixture
after one, 4 and 8 hours. These samples were precipltated
lnto one llter of water and soaked for 16 hours. The
samples were then dried in a desslcator over P205 at 1
Torr for 72 hours.
The samples were analyzed to determine the
relative concentration of the oxolanylene and oxirane unlts
in the polymer. The results were as follows:
Sample Mole ~ Mole % Mole %
Tlme Polyoxirane Polyoxolane Other*
201 hour 68 30 2
4 hours 24 73 2
8 hours 12 85 2
...
.i:
.. . .
*prlmarily vinyl
The samples and the epoxldized polybutadiene
startlng materlal (sample tlme = 0 hr.) were also analyzed
by differential thermal analysis to determlne the transltion
temperatures of the polymers. The reæults were as
follows: -
-22-
.~
Sample Mole % ~ole % Mole %
Time Polyoxlrane Polyoxolane Other Tg(C) Tm(C)
.. .. ..
0 hour 98 0 2 -12 80
1 hour 68 30 2 ~3 76
4 hours 24 73 3 19 77
8 hours 12 85 3 25 none
:
The ~oregolng shows that as the converslon of
oxirane units to 2,5-oxolanylene units lncreases, the glass
transitlon temperature (Tg) of the product increases.
These data further show that as the number of oxirane units
becomes small, the polymer ceases to exhlbit a melting
point (Tm). Thls is consistent wlth the conversion of the
oxlrane groups to 2,5-oxolanylene groups in the chain
reaction as prevlously explained.
Example 4
Polymers of the lnventlon prepared from
epoxldized in~ermedlate polymers in whlch the length of
;~ the B segments varies. ~
Two different polybutadlenes were employed as
precursors. The ~lrst ~içne (BDl) had an Mn of lI,000 and
comprised 9 mole p~rcent vinyl units, 38 mole percent
cls-1,4-butadiene units and 53 mole percent trans-1,4-
butadiene units. The second (BD2~ had an Mn of 98,000 and
comprises 98 mole percënt cis-194-b~u~adiene units and 2
mole percent 1,2-vinyl units.
The precursor polymers were epoxidized with
varylng stiochiometrlc concentratlons of peracetic acid
to achieve varying degrees of epoxidatlon, thereby
providing intermedlate polymers in which the median
/
length of the B segments varied widely. Epoxldation
was carried out in methylene chloride over a period
of about 6 hours using conditions similar to those
described in Example 2. The epoxidized polymers
were anlyzed by NMR to determine the relative concen-
tratlon of the various units in the polymer. The
precursor diene polymer and peracetic acid charges
used and the results obtained were as follows:
10 Charge ~ oxidized Polymer Composition
Polymer Peracetic Cis~ Cis"Oxi- 'ITrans"Oxi-
Lot (gms) Acid Vinyl diene(l) rane(2) rane(2)
I 100 BD2 229 2 29 69
II 100 BD2 310 2 9 89
15III 100 BD2 356 2 _ 98
IV 150 BDl 540 9 - 38 53
(1) Type III units
(2) Type II units
These epoxidized polymers were reacted (as
6-8 percent solutions by weighk in 90/10 dioxane/
methanol) at 80C. for varying periods of time in
the presence of a catalyst. The resulting polymers
were precipitated in distilled water and dried over
P205 at 0 Torr for 24 hours. Solutions of 0.2 percent
by weight of the pol~mers in CHC13 were prepared and
concentrated to removal all volatile impurities.
~ When the solutions had been concentrated to 10
; percent solids, thin films of the solutions were cast
onto tetrafluoroethylene sheets. The ~ilms were air
dried for 16 hours and vacuum dried over P205 at
1 Torr for 24 hours then redissolved in deuterochloro-
- 24 -
3~
form at 10 percent solids by weight and analyzed
by NMR to determine the relative concentrations of
the various units in the polymer The reaction times
and results were as follows:
Product Pol~mer Composition (Mole%)
Epoxidized Catalyst Rxn.
Polymer (Moles%) Time 1,2- 1,4 Oxolan-
Lot Lot (1) (hrs) diene diene Oxirane ylene Other
A I 10 24 2 28 49 13 8
B I 10 8L~ 2 29 36 22 12
C - II 10 24 2 9 20 56 14
D II 10 84 2 ~ 19 58 13
E II 25 24 2 9 16 59 15
F III 10 24 2 13 79 6
G III 10 84 2 _ 9 85 3
H III 25 24 2 - 7 87 5
I IV 10 24 8 - 28 54 9
J IV 10 84 8 - 24 62 9
(1) The mole percentages of the catalyst,
(CH3)4NOCH3, are based on the original
olefin content of the starting polydienes.
Less than ~0 percent Or the oxolanylene units
in polymers A and B are in segments in which at least
six such units are directly ~oined (as shown by statis-
tical analysis). Therefore polymers A and B do not
~ 25 fall within the present invention. The remaining
;~ ~ polymers (C-J) do fall ~ithin the invention, however.
These data demonstrate that the formation
,
of 2,5-oxolanylene units requires that the oxirane
groups be present in type _ segments, i.e. separated
by no more and no less than 2 main chain carbon atoms.
Thus, polymers prepared from epoxidized polymer I
~9 mole percent oxirane) greatly limit the conversion
of the oxirane units to oxolanylene units.
.,
- 25 -
s
3~4
The data further demonstrate that formation
of the oxolanylene units is the ma~or cause of the
reduction in oxirane units since, aside from the
formation of the oxolanylene units, there is relatively
llttle oxirane depletion. Thus, it is clear that the
ring expansion reaction wherein the oxolanylene units
are formed is a chain process in which a random
cleavage of an oxirane group initiates and promotes
the formation of 2,5-oxolanylene units. Furthermore,
the average length of the resultant oxolanylene units
bears a direct relationship to the average length of
the average oxirane segment.
Example 5
A polypropylene film rendered hydrophilic
by a coating of a polymer of the invention.
One part by weight of a polymer of the
invention prepared as described in Example 4F was
dissolved in 99 parts by weight isopropyl alcohol.
An oriented 2 mil polyproyplene film, having a water
contact angle of 100, was dipped into the polymer
~ solution and dried at 100C. for 10 minutes. The
;~ resultant coated film had a water contact angle of
30. The coated film was soaked in water for 16
hours and still maintained a contac~ angle of 30.
The coated film was then soaked in methyl alcohol
for 16 hours and still maintained a contact angle
of 30.
The coated film was inked with water-based
lnk, and the ink adhered thereto. The ink did not
- 26 -
i3~1~
adhere to uncoated polypropylene fllm.
Example 6
A polyester film rendered hydrophilic by a
coating of a polymer of the invention.
One part by weight of a polymer prepared
as described in Example 4F was dissolved in 99 parts
by weight of tetrahydrofuran. Polyester film having
a water contact angle of 67 was dipped into this
solution. The film was then dried in a 130C.
forced air oven for five minutes. The water contact
angle on the resulting coated film was reduced to
10.
This primed film demonstrated improved
adhesion to polar materials. The improved adhesion
was demonstrated by application of a strip of
pressure-sensitive tape to coated and uncoated
polyester film. The tape adhered only weakly to
the uncoated polyester film but adhered tenaciously
to the coated polyester film.
Example 7
Post-reaction o~ a polymer of the invention
~ with sodium sulfite to render it water-dispersible.
; A water-disperslble polymer according to
the invention was prepared by dissolving ten grams
of polymer F of Example 4 in a mlxture of 100 grams
of tetrahydrofuran and 100 grams of water at 60C.
Five grams of tetrabutyl ammonium bromide and 10 grams
of sodium sulfite were added to the solution and the
- 27 -
resulting mlxture reacted for five days with agita-
tion. The resulting polymer was water-dispersible
and thereby useful for coating from aqueous systems.
This water-dispersibility was achieved by the open-
ing of resldual oxirane groups in the polymer andthe addition of sulfo groups to the polymer at those
locations.
Post-reaction of a polymer of the invention
with dimethylamine to render it water-dispersible.
A water-dispersible polymer according to
. ~ .
the invention was prepared by dissolving ten grams
of polymer F of Example 4 in 100 grams of methyl
alcohol. Forty grams of a 40 percent by weight
solution of dimethyl amine in water was added to
the solution and the resulting mixture reacted for
three hours. A water-dispersible polymer was obtained
as a result o~ the opening of residual oxirane groups
in the polymer and the replacement of the oxirane
oxygen thereo~ by hydroxyl and amino groups. Nitrogen
analysis showed 3.8 percent N, indicating that 30
percent of the residual oxirane groups had been
converted to tertiary amino alcohol groups.
;~ Example 9
Gra~t copolymers accordlng to the inven-
tion.
- Two graft copolymers according to the
invention were prepared from the following
materials:
- 28 -
3~
A B
Polymer F of Example 4 3 grams 3 grams
Methylmethacrylate3 grams
Dodecylmethacrylate - 3 grams
Toluene 18 grams 18 grams
t-Butyl hydroperoxide 0. o6 gram 0. o6 gram
The solutions were placed in a sealed
vessel in an oxygen-free atmosphere and reacted
for 40 hours at 70C. The resulting polymers pro-
vided clear solutions and, when cast, clear films.
Sample B was analyzed in detail. A film
was dried at 1 Torr, redissolved in deuterochloro-
form and analyzed by proton MNR. The resulting film
comprised 46 mole percent polydodecylmethacrylate
segments and 54 mole percent of polymer 4F segments.
The solubility characteristics of the polymer demon-
strated that it was a graft p~olymer. Thus the pGlymer
was not soluble, although highly swollen, in
methanol. Methanol is a solvent for poly-2,5-
oxolanylene but is not a solvent for polydodecyl-
methacrylate. Moreover, less than 10 weight percento~ the polymer could be extracted with methanol.
Additionally, the polymer was not soluble in hexane.
Hexane is a solvent for polydodecylmethacrylate
but is not a solvent for poly-2,5-oxolanylene.
Again, less than 10 weight percent of the polymer
; could be extracted with hexane. Furthermore, the
polymer was soluble in solvents for both segments
such as toluene, tetrahydrofuran and chloro~orm.
- 29 -
Example 10
Compatible blends of a polymer of the inven-
tion with thermoplastic polymers.
The polymer of sample F of Example 4 was
dissolved in tetrahydrofuran to form a 6 percent by
weight solution. Separate portions of the solution
were added to solutions t10 percent by weight in
`~ tetrahydrofuran) of various thermoplastic resins.
The resulting solutions were clear. The solutions
were poured into separate petri dishes and allowed to
air dry for sixteen hours. The drled samples were
then placed in a forced air oven at 100C. to drive
off any residual solvent. The resulting samples
were clear and flexible. The glass transition
temperature of the samples was measured by differen-
tial thermal analysis. The results of the transitiontemperature determinations are listed below:
Polymers Weight Ratio Tg(C)
-~ Polymethylmethacrylate 100 102
(PMMA)
Polyvinylchloride100 81
(PVC)
Poly-2,5-oxolanylene 100 25
~ (POX)
; PMMA/POX 50/50 55
PVC/POX 50/50 52
PMMA/POX 75/25 65
PVC/POX 75/25 72
In all cases only a single glass transition
temperature was noted. The film clarity, flexibility
- and glass transition temperature data (i.e. a single
- 30 -
Tg which is intermediate between the parent polymers)
are convincing evidence of compatible polymer blends.
Example 11
Compatible blends o~ a polymer of the
invention with epoxy resins.
Polymer I of Example 4 was used to form
compatible mixtures with various epoxy resins. The
mixtures were applied to a vinyl surface and cured
to^form coatings. The following formulations were
prepared and applied:
Polymer I Epoxy Resin Photoactivator(3) Solvent(4)
Lot (grams) (grams) (grams) (grams)
A 0-05 0.45 (1) 0.025 5
B 0.1 0.4 (1) 0.025 5
C 0.2 0.3 (1) 0.025 5
D 0.3 0.2 (1) 0.025 5
E 0.4 0.1 (1) 0.025 5
F 0.1 4 (2)s 0.025 5
(l) o~H 2-0-C ~ ~o
20~ Epoxy equivalent weight (EEW) 133.
(2) ~ -CH20-C-~-CH2 ~ C~ -C ~ o
Epoxy equivalent weight 213.
(3) Four parts diphenyliodonium hexafluoro-
phosphate and one part 2-chlorothioxanthene.
(4) Tetrahydrofuran.
- 31 -
.
~63~4
After coating, the solutions were allowed
to air dry 16 hours and then 10 minutes in a 100C.
forced air oven. At this point the coatings were
clear and tacky. The coatings were then photocured
by placing them 10 centimeters away from a sunlamp
(250 W. - General Electric) for five minutes. The
cured coatings remained clear and demonstrated
increased flexibility, adhesion and solvent resis-
tance (resistance to methyl ethyl ketone) when
compared to control coatings containing no poly-2,
5-oxolanylene.
Example 12 -
Compatible blend of a polymer of the inven-
tion with a thermosetting polyester resin.
Polymer F of Example 4 was added to a free
radically curable thermosetting polyester resin. The
following mixture was prepared:
Polymer F 10 grams
Styrenated polyester resin* 1 gram
Benzoin ethylether 0.01 gram
. -- ,
~Polyester of 1 mole isophthalic acid,
1 mole maleic acid and 2.2 moles pro-
pylene glycol. The resin is 1 part
styrene to 2 parts polyester.
The clear solution was cast onto a poly-
ethylene terephthalate film, and the solvent was
driven of~ by drying in a 100C. oven for 10 minutes.
The resulting clear and tacky film was exposed to a
250 W. sunlamp at a distance of 10 centimeters for
- 32 -
3~
ten minutes. The resulting fllm was a perfectly clear,
leathery material having excellent adhesion to the
polyester film. When the polyester resln alone was cured
wlth benzoin ethyl ether, a brittle, glassy film was
obtained which had poor adhesion to the polyester film.
