Note: Descriptions are shown in the official language in which they were submitted.
CA 02335800 2000-12-19
_... ."..~.,.as,
WO 00/01876 PCTNS99114676
TITLE
POLYVINYL ALCOHOL) COPOLYMER IONOMERS, THEIR
PREPARATION AND USE IN TEXTILE SIZES
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to compositions which are particular
polyvinyl alcohol) copolymer ionomers, a process to prepare those
compositions, and textile sizes based on those compositions. It also relates
to
sizes based on blends of those ionomers with other polyvinyl alcohol) polymers
or starches. The compositions are polyvinyl alcohol) copolymers which have
carboxyiate salt ionomer comonomer units. Desizing sizes of these ionomers or
blend sizes containing these ionomers, in either water or caustic solutions is
easier than desizing sizes based on polymers or polymer blends which contain
no polyvinyl alcohol) copolymer ionomer.
Discussion of Related Art
Polyvinyl alcohol) hompolymers, and certain polyvinyl alcohol}
copolymers, with comonomers such as alkyl acrylates, have been known for use
as textile sizes for many years. For convenience, both will be generically
referred to hereinafter as PVA polymers. When specificity requires they will
be
2 0 referred to as PVA homopolymers and PVA copolymers. By convention, PVA
homopolymer includes PVA polymer derived from homopolymer polyvinyl
acetate) which has been only partially 'hydrolysed' or 'saponified', as well
as that
which has been'fully' (>98%} hydrolysed. The terms 'fully hydrolysed PVA
homopolymer' and 'partially hydrolysed PVA homopolymer' will be used if
2 5 distinction is necessary. It is also possible to have fully or partially
hydrolysed
PVA copolymers. Indeed, certain partially hydrolysed copolymers have found
specific use as sizes for hydrophobic fibers, as noted below.
Different PVA polymers differ quite significantly in properties as
textile sizes and in the ability of fabrics sized with them to be desized.
This
3 0 difference primarily depends on the degree of saponification or
hydrolysis, the
particular comonomer, and the comonomer content. Other factors including
molecular weight and thermal history can also be important in size
characteristics.
PVA polymers are generally prepared by alcoholysis or
3 5 hydrolysis of the corresponding polyvinyl acetate) homopolymer or
copolymer.
Strictly, alcoholysis, carried out with a basic catalyst, leads to the
corresponding
CA 02335800 2000-12-19
WO 00/01876 PCT/US99114676
alkyl acetate and the polyvinyl alcohol) unit, and is conducted in alcohol as
reaction medium. Hydrolysis, in water, generally uses larger amounts of
metallic, caustic base, leading to the corresponding metal acetate rather than
alkyl acetate, and the polyvinyl alcohol) unit. Formation of metal salts, i.e.
acetates, has led to use of the term 'saponification' for the process. akin to
formation of metal salts of fatty acids with caustic, in forming soaps. When
aqueous alcohol is used as the reaction medium both hydrolysis and alcoholysis
may occur. However, US 2,940,948 discloses that under specific circumstances,
even with aqueous alcohol , alcoholysis rather than hydrolysis occurrs. While
1 o the distinction strictly depends on reaction products, the terms have
tended to be
used non-rigorously. The product are typically referred to as'hydrolysed' or
'saponified'.
It is common to use the term 'partially hydrolyzed' or 'partially
saponified' when not all the acetate groups are completely converted to
alcohol
groups. When homopolymer polyvinyl acetate) is only partially hydrolysed,
the resulting PVA is strictly a vinyl alcohol/vinyl acetate copolymer.
However,
as noted, such polymers are generally referred to as PVA homopolymers. The
term copolymer in this regard is usually reserved for materials which result
from
hydrolysis of the corresponding vinyl acetate copolymer, i.e. polymer also
2 0 containing units derived from a monomer other than vinyl acetate, such as
an
alkyl acrylate.
Fully hydrolysed PVA homopolymer is highly crystalline and
strong, but because of its high crystallinity it dissolves only in hot, not
cold
water. Furthermore, when it is subjected to high temperatures, it can develop
2 5 even higher levels of crystallinity than as prepared, resulting in polymer
which
is even more difficult to dissolve. Finishing mills with certain fabrics,
particularly blend fabrics, tend to use a heat setting condition to relieve
fiber
stress. The treatment i~typically carried out at temperatures which develop
further crystallinity in fully hydrolysed PVA hornopolymer, so that when such
3 0 polymer is used as size on fabric, the treatment causes an increase in its
crystallinity and a decrease in ease of subsequent desizing.
PVA copolymers and partially hydrolysed PVA homopolymers
are less crystalline, and dissolve at lower temperatures, or more rapidly at a
given temperature. As a result they desize in water more readily, and are less
3 5 subject to change in crystallinity and ability to be desized with fabric
heat-
CA 02335800 2000-12-19
WO 00!01876 PCT/US99/14676
setting treatments. For a given level of comonomer or residual non-hydrolyzed
acetate units however, the two types of PVAs are not identical in several
respects. This is partly because the distribution of comonomer units (or units
derived from them by lactonization, as discussed below) along the polymer
chain is not the same as the distribution of residual acetate units along the
chain
after partial hydrolysis. One difference, for instance, is that acetate units
tend to
be blocky, and blockiness of partially hydrolysed PVA causes more surfactant
behavior and more foaming when used as size. Furthermore, differences in the
conditions used for hydrolysis/saponfication of a given copolymer,
particularly
physical differences such as degree of agitation and kneading of precipitating
product, have also been disclosed as producing differences in partially
hydrolysed products.
Various PVA copolymers have been disclosed as being useful for
textile sizes. In 1972, U.S. Patent No. 3,689,469 (Inskip et al.) disclosed
PVA
copolymers with 2 to 6.5 weight percent methyl methacrylate as comonomer
which are useful as textile sizes, and compared their properties as sizes with
fully hydrolysed and partially hydrolysed PVA homopolymer. The disclosure
indicated however, that above about 6 weight percent methyl methacrylate such
copolymers are excessively water soluble.
PVA copolymers containing 1 to 10 mole percent methyl acrylate
or methyl methacrylate as comonomer are disclosed in U.S. Patent No.
4,990,335 (Bateman et al.). (For methyl acrylate this corresponds to about 2
to
16 weight percent methyl acrylate in the polymer, calculated as non-lactonized
vinyl alcohol copolymer). The polymers were not disclosed as being useful for
2 5 sizes.
However, in a recent US Patent 5,362,515 (Hayes et al, issued
11/8/94), polymers with high acrylic or methacrylic ester comonomer levels
(above Inskip's comonomer levels and in the top range of Bateman's comonomer
levels, such as from 7 to 15 weight percent of methyl (meth)acrylate), were
3 0 disclosed as useful in a process to produce textiles which used these
polymers
for sizes. The polymers are disclosed as being very readily desized,
particularly
with caustic solutions.
Polyvinyl alcohol) copolymers where the comonomer directly
provides an acid functionality are known. The acid functionality may derive
3 5 from a copolymerized monocarboxylic, dicarboxylic acid, or a dicarboxyiic
acid
3
CA 02335800 2000-12-19
WO 00/01876 PCT/US99114676
half ester. Acid functionality, however, can result from hydrolysis of ester
comonomer units, such as an alkyl acrylate or methacrylate. Depending on the
precise conditions, such as the catalyst, its concentration, and the solvent
medium used to hydrolyze/saponify the vinyl acetate ester units in the vinyl
acetate copolymer, the other ester units, i.e., the comonomer ester units may
or
may not also be hydrolysed to the corresponding acid. Generally, the vinyl
acetate ester units are far more readily hydrolysed than alkyl ester units. If
the
alkyl ester units are also hydrolysed, and if enough base is present, the
resulting
acid units may also be neutralized to become ionomer units.
Under some conditions, internal trans-esterification can take
place between the vinyl alcohol units resulting from hydrolysis, and the alkyl
ester units, resulting in in-chain lactone units. Because both the vinyl
acetate
ester units, and the alkyl carboxylic acid ester units are subject to
hydrolysis,
and the hydrolysed alkyl ester ~~:.its can be neutralized, depending on
precise
conditions, a large number of possible hydrolysis products are possible.
As noted, if base in sufficient quantities is present, under some
saponification conditions any acid units present from an acid comonomer, or
resulting from hydrolysis of ester comonomer, may be neutralized to form
carboxylate salts (ionomer) units. However, if the solvent conditions throw
the
2 0 PVA polymer out of solution, it may be that ionomer units are not present
in the
isolated polymer. In view of the complexity of the situation, it is not
surprising
that in many references, it is not at all clear, and certainly not stated,
whether
isolated polymer contains any ionomer units - even though reaction conditions
might appear to allow formation of such units.
Polyvinyl alcohol) copolymer ionomers containing specific
levels of acid/ionomer units, often with a limit to the degree of
saponification/hydrolysis of the vinyl acetate ester units, have been
described for
use as sizes for different materials including paper, and textiles.
Use of certain pcly(vinyl alcohol) copolymers which contain
3 o ionomer units, for use as sizes specifically for hydrophobic fibers, is
known.
Japanese Patent publication No. 55-44191 (11/I 1/80, layed open 49-66988,
6/28/74) discloses partially saponified copolymers of vinyl acetate containing
from 0.1 to 10 mole percent monoalkyl maleate for use as such a size. The
level of saponification must be between 50 and 80 percent, or adhesion to the
hydrophobic fibers is inadequate, and even cohesive behavior is disclosed as
4
CA 02335800 2000-12-19 ~°w-
WO 00/01876 PCT/US99/14676
declining. Alkaline salts of the monocarboxylic ester PVA copolymer are
specifically disclosed as part of the invention. The comonomer unit in the
precursor polymer rnust be a ir.cnoalkyl maleate. Sizing solutions of the
polymer are disclosed.
Japanese Patent publication No. 60-14148 (4/11/85, layed open
53,134990, 11/25/78) describes a sizing material which is also a low
saponified
(65-90 mole percent) vinyl acetate copolymer - in this case the saponified
product of a vinyl acetate/monocarboxylic acid copolymer with up to 3 mole
percent acid. The product is again specifically useful for hydrophobic
materials.
More than 3 mole percent is disclosed as producing excessive hygroscopicity,
lack of cohesiveness, and poorer weaving efficiency when used as a size. The
product is produced by saponification at a low temperature in alcohol, water
or
aqueous alcohol, using either metal alcoholate or hydroxide, but under very
specific conditions, specifically without kneading or mixing while solid
product
is obtained. Example polymers contain 0.8 mole percent acid or less, and a
molar excess of base. However, there is no indication given of metal
hydroxylate (ionomer) groups in the isolated saponified polymer.
Japanese Patent publication No. 60-31844 (7/24/85 layed open
53-91995, 8/12/78) describes production of PVA copolymers containing from
2 0 0.1 to 50 mole percent of a dicarboxylic acid unit from a dicarboxylic
acid
monomer. It is disclosed that the polymers, produced by a special process are
better than prior art acid copolymers for uses such as paper strengtheners,
fiber
sizing agents and adhesives. The special process is a solution process which
allow solubility throughout the polymerization, by controlling dicarboxylic
acid
2 5 concentration, in conjunction with a saponification which uses two moles
of
alkali per mole of dicarboxylic acid plus 0.1 to 1.0 mole per mole of vinyl
acetate. While there is thus a large amount of base, the disclosure
specifically
refers to avoiding any alkali remaining in the saponified PVA polymer. It
would thus appear the saponified product does not contain metal carboxylate
3 0 units.
US Patent No. 4,747,976 (Yang et al.) discloses water soluble
film pouches containing detergent for use in washing of clothes. The films are
PVA copolymers containing icromer units which derive from various
comonomers which include methyl acrylate and methacrylate. The comonomer
3 5 concentration in the polymer before saponification is from 2 - 6 mole
percent.
5
CA 02335800 2000-12-19
WO 00/01876 PCT/US99/14676
Of the comonomer units. it appears that only I to 5 percent of them are
converted to ionomer units. The disclosure ambiguously refers to 'converting
about 1 to 5 mole percent of the comonomer to anionic comonomer'.
Presumably this means the final polymer has a maximum of ~ percent of the
acrylate or methacrylate units converted to anionic units. or a maximum of 0.3
mole percent anionic units in the in the final polymer.
Desizing typically involves water washing. However desizing of
particular polymers with caustic solution is also well known and has been
described. The above-mentioned Japanese patent publication 60-14148, for
1 o instance, uses sodium carbonate solutions as desizing agents.
Solubility and dissolution times of various types of PVA polymer
in water and caustic solutions are discussed in 'Polyvinyl Alcohol', John
Wiley
& Sons Ltd., 1992, Chapter 1 l, p365-368. It is noted there that partially
hydrolysed PVA homopolymer dissolves more slowly in caustic solutions than
in water, whereas PVA copolymers with methyl methacrylate as comonomer
dissolve more rapidly in caustic than in water. This is explained by the fact
that
caustic further hydrolyses partially hydrolysed PVA to homopolymer, whereas
with the copolymer, lactone rings which may be present derived from the
comonomer, are hydrolyzed, resulting in ionic groups which are highly soluble.
2 o Alternatively, if free acid rather than lactone units are present, they
are
neutralized to form ionomer units.
Many other materials are known for use as textile sizes.
Unmodified starches are inexpensive, but they do not generally have as good
properties as PVA polymers, often flaking off the yarn when used as sizes.
2 5 They do not give stable solutions, and often desizing requires use of
enzymes.
Many modified starches are known which are improvements in various ways
over simple starches, but may be considerably more expensive. Polyacrylic
sizes are also known and have good properties, but are extremely water
sensitive.
3 o Blending different sizing materials is known and used. It is well
known that blending can provide properties of the size itself, and economics,
intermediate between those of the components. The polymers described in US
5,362,51 S noted above, have been disclosed as useful as sizes in mixtures
with
other PVA polymers in US Patent No. 5,436,292 (Hayes et al. issued 7/25/95),
3 5 and with starches in US Patent No. 5,405,653 (Hayes et al. issued
4/11/95).
CA 02335800 2000-12-19.
WO 00/01876 PCT/US99/14676
Blending the readily desizable polymers of above US 5,362,515 with starches
and other PVA polymers was disclosed as a means of enhancing desizability.
These three patents are hereby incorporated by reference.
While it is clear that the mechanism of desizing using caustic
solutions can involve in-situ formation of ionomeric species in the PVA
copolymer (as with the Hayes reference PVA copolymers), there appears to be
no consideration of use of PVA copolymer ionomers which are highly
hydrolysed with respect to vinyl acetate units in precursor polyvinyl acetate)
copolymer, as sizes per se, in their own right, or as desizing enhancers in
blend
compositions.
Ease of desizing can strongly affect the economics of fabric
production. While many sizing materials are known, each having its particular
niche, there remains a need for yet further size materials which are even more
readily desized, and which have acceptable mechanical properties, and give
stable size solutions. There particularly remains a need for even more highly
desizable size materials than known materials, because they can be used to
upgrade the desizability of those known materials, even when added to those
known size materials at quite low levels. In such upgrading uses, any less
desirable characteristics of highly desizable materials, such as
hygroscopicity
2 o which can lead to tackiness, is minimized in the overall composition when
only
low levels of the highly desizable material are required.
SUMMARY OF INVENTION
The invention concerns new sizing compositions which are
2 5 improvements over those described in the above cited Hayes et al. patents.
The
sizing compositions are aqueous solutions of a polymer or polymer blends
including that polymer, the polymer being a PVA copolymer ionomer having a
controlled level, from 0.1 to 10 mole percent of anionic carboxylate (ionomer)
units. Fabrics sized with such sizes are able to be very effectively desized
3 o compared with the known size materials.
More particularly, the present invention provides a sizing
solution, comprising:
a 1 - 20 weight percent aqueous polymer solution comprising, a
first polymer which is from greater than 90 up to 100 percent hydrolysed, with
3 5 respect to vinyl acetate ester units remaining from precursor vinyl
acetate
CA 02335800 2000-12-19
WO 00/018?6 PCT/US99/14676
copolymer, polyvinyl alcohol) copolymer ionomer, the copolymer ionomer
having from 0.1 to 10 mole percent anionic carboxylate salt units.
The sizing solution may further comprise:
a second polymer, in an amount from 10 to 90 weight percent,
based on the weight of total first and second polymer, the second polymer
being
a non-ionomeric polyvinyl alcohol) polymer which is a polyvinyl alcohol)
homopolymer, or a polyvinyl alcohol) copolymer containing up to 15 weight
percent units derived from a C 1-C8-alkyl (meth)acrylate or a C 1-C3-dialkyl
fumarate or maleate.
l0 The size solution may further comprise, in addition to the first
polymer only:
a third polymer in an amount from 10 to 90 weight percent with
respect to total first and third polymer, the third polymer being a starch
which is
a natural starch, a Synthetic starch. a physically modified starch, or a
chemically
modified starch.
A further aspect of the invention is a process to prepare
polyvinyl alcohol) copolymer ionomers having from 0.1 to 10 mole percent
ionomer units, from corresponding polyvinyl alcohol) copolymers containing
from 0.1 to 10 mole percent of a C1-C8-alkyl (meth)acrylate or Cl-C3-dialkyl
2 0 fumarate or maleate comonomer derived units, by full or partial hydrolysis
with
base, of those comonomer units, in a reaction medium which either allows the
polyvinyl alcohol) copolymer starting polymer and derived ionomer to remain
undissolved as a slurry, and hence capable of being isolated as a solid
granular
polymer, or in a reaction medium which is a solvent for the derived ionomer,
2 5 leading directly to solutions useful as sizes.
DETAILED DESCRIPTION OF THE INVENTION
In this disclosure, it should be understood that the use of the term
comonomer, when referring to PVA copolymers, as used here and as
3 0 conventionally used, refers to the comonomer copoiymerized in the
polyvinyl
acetate) copolymer before the latter is converted to a PVA copolymer by
alcoholysis/hydrolysis/saponification.
The terms hydrolysis or saponification will be used to encompass
conversion of the vinyl acetate ester units in poly(vinyi acetate) to
polyvinyl
3 5 alcohol) units, even if the reaction is strictly an alcoholysis. The term
hydrolysis
8
CA 02335800 2000-12-19
WO 00/01876 PCTNS99/14676
will also be used for conversion of ester units of the alkyl or dialkyl ester
comonomer units to free acid units, and for conversion of lactone units (i.e.,
internal ester units) to free acid units. When acid units are converted to
ionomer
units with base, the usual term 'neutralization' will be used, or 'partial
neutralization' if not all acid units are neutralized. In addition, when
referring to
polymer, the well known term'ionomer' (typically used for ethylene copolymer
ionomers), as well as the term'ionomerization' will be used. The ionomer units
are anionic carboxylate units or salt units, and all these terms will be used
interchangeably.
l0 PVA copolymers are prepared by hydrolysis/saponification of
the corresponding polyvinyl acetate) copolymer, containing the same
comonomer. The polyvinyl acetate) copolymer will be referred to as the
'precursor' copolymer. PVA copolymers ionomers are prepared from PVA
copolymers with comonomer units by hydrolysis andlor only neutralization
(depending whether the comonomer is an acid or alkyl ester which first has to
be
hydrolyzed). The PVA copolymer, before ionomerization, will be referred to as
the 'starting' copolymer to avoid confusion with the precursor acetate
copolymer.
The polymers of the invention are referred to as polyvinyl
alcohol) copolymer ionomers, PVA copolymer ionomers or, for convenience,
simply ionomers. When the term PVA copolymer alone is used, polymer
without ionomer units is being referred to. The term PVA copolymer ionomer
however embraces polymers which may contain both some remaining non-
hydrolysed vinyl acetate units, and in addition, may especially contain
remaining lactone (internal ester) units and/or remaining methyl acryiate or
2 5 methacrylate ester units which have not been hydrolysed.
In PVA copolymers, it is well known that ester comonomer units
are subject to reactions with a hydroxyl from an adjacent vinyl alcohol unit
to
form lactones, and free alcohol from the ester unit. Thus an original ester
monomer unit may no longer exist as the same entity as was present in the
3 0 precursor polyvinyl acetate) copolymer. Almost complete lactonization may
occur, though the extent may vary with different comonomers and hydrolysis
conditions. The use of phrases such as PVA copolymers'with' or'containing' a
given comonomer and the like should be understood in this context.
9
CA 02335800 2000-12-19 ,.,"
WO 00101876 PCTNS99114676
Starches are polymeric and are referred to as'polymers' in this
disclosure, though of course they are significantly different types of
polymers
from strictly synthetic polymers such as PVA polymers.
It has now been discovered that PVA copolymer ionomers are
uniquely useful in preparing textile sizing compositions. This is because of
their
extraordinarily ready ability to be desized both in water and in dilute
caustic
solutions. They are far more readily desized that the PVA copolymer
compositions of comparable comonomer content, described in US Patent
5,362,515 previously referred to.
1 a In addition, sizes based on blends of PVA copolymer ionomers
with either prior art PVA polymers or starches both previously known for use
as
size materials, may be more readily desized than many comparable PVA
polymer blends which do not contain PVA copolymer ionomer. Because the
PVA copolymer ionorners are so readily desized, they will be usable at
relatively low levels in blends with other PVA polymers or starches, and
achieve
a significant improvement in desizability, without adding any substantial
disadvantages which may result from the PVA copolymer ionomer. In blends
therefore, the PVA copolymer ionomers can be used in low amounts, as'ittle as
10 percent, rather than a major blend component. Of course in many instances.
2 o depending on the starch or PVA polymer to be blend modified, high levels
of
PVA copolymer ionomer may be advantageous.
The sizes of this invention may be solutions of PVA copolymer
ionomer alone, PVA copolymer ionomer and non-ionomeric PVA polymer,
PVA copolymer ionomer and starch, or PVA copolymer ionomer with both non-
ionomeric PVA polymer and starch. The PVA copolymer ionomer of this
invention can be a mix of PVA copolymer ionomers each having a different
composition, within the defined limits. Likewise non-ionomeric PVA polymer
can include mixtures of ion-ionomeric PVA polymer within the defined limits.
Starch can likewise include mixtures of starches. The terms PVA copolymer
3 0 ionomer, non-ionomeric PVA polymer and starch, as used in the claims,
should
be understood to include mixtures in the above sense.
The PVA copolymer ionomers of this invention are derived from
polyvinyl acetate) copolymers with a comonomer unit which is capable of
being converted to an ionomer unit. The vinyl acetate units in the precursor
3 5 polymer are highly saponified/hydrolysed, being at least 90 % hydrolysed,
CA 02335800 2000-12-19 :.,.~.
WO 00101876 PCT/US99/14676
preferably 95 % hydrolysed, and can be 'fully' hydrolysed. In preparing the
ionomers from the starting PVA copolymer, the ionomerization reaction using
base, to act on the alkyl ester units, will also act to hydrolyze remaining
vinyl
acetate units. It is believed that vinyl acetate ester units will in fact be
preferentially hydrolysed over alkyl ester units, and few vinyl acetate units
will
remain. However, when the amount of base used in the ionomerization reaction
is small because only a low mole percent ionomer units is desired in the
ionomer, it is likely that some vinyl acetate units will survive. For all
ionomers,
the mole percent vinyl acetate units remaining will be less than 10 percent,
1 o corresponding to greater than 90 percent hydrolysed precursor vinyl
acetate
units. In ionomers with more than 2 mole percent ionomer units, it is likely
that
at least 95 percent of vinyl acetate units will have been hydrolysed to vinyl
alcohol units, and probably more than 98 percent will have been hydrolysed.
However no attempt has been made to accurately measure the level of remaining
vinyl acetate units. These low levels of remaining vinyl acetate units are in
marked contrast to ionomers produced from precursor polyvinyl acetate)
carboxylic acid or monoalkyi maleate copolymers discussed in the prior art
section. In these polymers, ionomer units will be formed by neutralization of
the acid units, and the vinyl acetate units apparently remain, and indeed are
2 o required for the utility disclosed. Hence the relatively low level of
vinyl acetate
hydrolysis in those polymers.
The ionomers of this invention are, generally, highly suitable for
hydrophilic fibers. However, because the level of ionomer units can be as low
as 0.1 mole percent, they will also be suitable for hydrophobic fibers. The
ionomers can be used in blends with other PVA based or starch sizes, and in
blends, their utility for different fibers can be varied depending on the
other
component and the level of ionomer in the blend. The level of ionomer units
can be varied from 0.1 to 10 mole percent, but is preferably from 2 to 8 mole
percent. In blends, the effective amount of ionomer units, overall, can be
3 o varied both by varying the number of ionomer units in the PVA copolymer
ionomer in the blend, and by varying the amount of the PVA copolymer
ionomer in the blend. Thus the most suitable composition for a fiber of given
hydrophobicity or hydrophilicity can be obtained by varying the percent of
ionomer units in the PVA copolymer ionomer, as well as the proportion of the
3 5 PVA copolymer ionomer in the blend. Within the bounds of the invention
m
CA 02335800 2000-12-19
WO 00/01876 PCT/US99/14676
therefore, there we many variables which may be altered, and hence great
versatility in achieving maximum suitability. While considerable trial and
error
might be involved, it is nevertheless within the skill of the artisan to
determine
an optimum composition which will give closest to the desired size properties
and the desired desizability.
Still other composition variables in the PVA copolymer ionomer
can be manipulated independently of the number are the molar percent of
ionomer units. Thus the number of methyl alkyl (meth)acrylate comonomer
units (or twice the number in the case of alkyl maleate/fumarate units) in the
1 o precursor PVA copolymer can be higher than the number of ionomer units in
the
derived PVA copolymer ionomer, since complete hydrolysis of those ester units
('ionomerization') is not necessary. As noted, unconverted alkyl ester or
derived lactone units can remain. There are therefore a large array of
variables
within the compositions of the invention which can be adjusted to suit a given
fiber.
In blend compositions tested, it has been found that the ease of
desizing is, very approximately, a weighted average of the ability to desize
the
blend components, rather than being limited by the Least readil; ~ desized
component. This means that if a particular quality of a size material is
desired -
2 o a particular property, or low cost for instance - in a size material that
is difficult
to desize, then a blend with PVA copolymer ionomer may offer an ideal
compromise between properties and ability to desize. Of course, the easiest
way of changing ionomer content in a blend size composition is merely to
change the amount of the PVA copolymer ionomer in the composition, rather
than changing the nature of the PVA copolymer ionomer. The higher the
amount of ionomer functionality in the PVA copolymer ionomer the smaller the
amount required to introduce a particular amount of ionomer function into a
blend. This may allow any advantageous size properties of the non-ionomer
component of the blend to be more dominant.
3 o The PVA copolymer ionomers of this invention may be made
from any P V A copolymer containing a comonomer unit which can be converted
into an ionomer. Thus the comonomer unit can be a free carboxylic acid or
dicarboxylic acid unit, which is simply neutralized to form the corresponding
ionomer. However, it is preferable to avoid free acid comonomers, and the
3 5 presence of free acid. This is preferred because free acid comonomers will
12
CA 02335800 2000-12-19
WO 00/Ot876 PCTNS99/14676
consume the alcoholysis/saponification catalyst. A far preferable method of
preparing the copolymer ionomers is by preparation from PVA copolymers
containing an alkyl acrylate or a dialkyl dicarboxylate, so that no free acid
remains in the polymer. In addition, some ester units (either external as
acrylate
or internal as iactone) can remain, addition composition versatility. The PVA
copolymer containing such a monomer will be made from the corresponding
polyvinyl acetate) copolymer.
The preparation of PVA copolymer ionomers from such
monomers then, involves a series of processes, some of which are well known in
1 o the prior art, but which are enumerated and quantified here for clarity.
1. Preparation of polyvinyl acetate) copolymers containing a
C1-C8-alkyl (meth)acrylate or C1-C3-alkyls dialkyl maleates or fumarates. The
comonomer is preferably an alkyl (meth)acrylate, and most preferably methyl
acrylate. The molar amount of comonomer in the vinyl acetate copolymer must
obviously be at least as great as the molar amount of ionomer units required
in
the final PVA copolymer ionomer if an alkyl ester of a monocarboxylic
comonomer is used, (or half as great if a dialkyl ester of a dicarboxylic acid
is
used, since there are potentially two ionomer units derivable from each
comonomer unit). However the molar amount in the polyvinyl acetate)
2 o polymer can be greater. The molar amount of ionomer units suitable in the
finally derived PVA copolymer ionomer is from about 0.1 to about 10 % when
used for a size composition. Levels above 2 percent are preferred for use as
sizes. Above 10 percent, excessive water sensitivity can begin to be apparent.
If an ionomer with 10 mole percent ionomer units is required, the precursor
2 5 vinyl acetate copolymer must, for an alkyl monocarboxylic ester comonomer
such as methyl acrylate, contain 10 mole % of that comonomer, or 5 mole
percent of a dialkyl fumarate or maleate.
In the art it is common for comonomer levels to be quoted in
weight percent. In this regard, for the preferred monomer, methyl acrylate,
since
3 o methyl acrylate and vinyl acetate have the same molecular weight, for the
vinyl
acetate/methyl acrylate precursor copolymer, 10 mole percent methyl acrylate
corresponds to 10 weight percent. For methyl methacrylate the weight percern
would be closer to 11 weight percent, and for higher alkyl (meth)acrylates,
weight percent would of course be higher still. Note however, for a given mole
3 5 percent comonomer, the weight percent of that comonomer in the resulting
PVA
13
CA 02335800 2000-12-19 4, ",.",~..,.
WO 00/01876 PCT/US99/14676
copolymer (calculated as that comonomer rather than weight based on any
derived lactone) will be much greater than in polyvinyl acetate) precursor
copolymer, because of the lower molecular weight of the vinyl alcohol unit. As
an example, a 90/10 weight or mole percent polyvinyl acetate/methyl acrylate)
copolymer would give a 90/10 mole or about 80/20 weight percent polyvinyl
alcohol/methyl acrylate) copolymer.
Whatever the original mole percent alkyl acrylate units in the
precursor polyvinyl acetate) copolymer, only 0.1 mole percent ionomer units
need be present in the finally derived PVA copolymer ionomer. For size
compositions. at least 2 mole percent ionomer units are preferred. Normal
trial
and error can be used to determine, for a given utility, whether it is better
to
have excess (i.e., non-ionomerized) alkyl ester units in the PVA copolymer
ionomer or not.
2. Hydrolysis/saponification of the polyvinyl acetate)
copolymer either partially or fully to the corresponding polyvinyl alcohol
copolymer, e.g., preferably polyvinyl acetate)/methyl acrylate to polyvinyl
alcohol)/methyl acrylate. The degree of hydrolysis should be above 90 percent
and can approach 100 percent to the extent that this i : achievable. Typically
99
to 99.8 percent is achievable. Preferably the degree of hydrolysis is above 95
2 0 percent. In many cases, depending on precise conditions, if the ionomer is
being
prepared by hydrolysis of alkyl ester comonomer in a PVA/alkyl ester
copolymer, if that copolymer is only partly hydrolysed/saponified (with
respect
to the vinyl acetate units in the precursor polyvinyl acetate) copolymer
precursor, further hydrolysis of the vinyl ester units together with the
desired
2 5 hydrolysis and ionomerization of the alkyl ester units will also occur.
While polyvinyl acetate) polymers and copolymers have utility
in their own right, and therefore are isolated as such, a considerable portion
of
such polymers and copolymers are used specifically for PVA production. It is
possible to carry out polyvinyl acetate) preparation and saponification
without
3 o isolating the polyvinyl acetate) polymer. Thus, U.S. 2,940,948 describes a
process where the polyvinyl acetate) homopolymer slurry directly as prepared,
is directly hydrolysed to PVA polymer. The process would equally apply to
polyvinyl acetate) copolymers In other words, the two steps 1 and 2 are
combined without any polymer isolation in between. In principle, step 3 below,
3 5 conversion to ionomer could be carried out without isolation of PVA
polymer,
14
CA 02335800 2000-12-19 ..:.....
WO 00/01876 PCT/US99/14676
so that it is possible to have a combined process which combines polyvinyl
acetate) copolymer preparation, hydrolysis, and ionomerization, without ever
isolating either the polyvinyl acetate) copolymer, or the PVA copolymer. Even
the resulting PVA copolymer ionomer may be made directly into size solution
without its isolation as polymer. The process which is part of the present
invention however, is concerned only with the step of converting granular PVA
copolymer into PVA copolymer ionomer. This is referred to as step 3.
3. Conversion (hydrolysis and neutralization in the same step) of
the PVA copolymer to partial or fully ionomerized PVA copolymer ionomer.
1 o This step is described in detail below.
Typical preparation of such polyvinyl acetate) copolymers, (i.e.,
step I ) and their hydrolysis is given in U.S. Patent No. 3,689,469 which
describes laboratory scale preparations, and U.S.4,900,335 which describes a
continuous process for such polymerizations, for copolymers with up to 10 mole
percent alkyl (meth)acrylate. In preparation, the amounts of monomer in the
feed are adjusted for different levels required in the polymer, and for their
different reactivities. These two patents are hereby incorporated by
reference.
Methacrylates are more reactive than acrylates, but both are far
more reactive than vinyl acetate, so that typically they are completely
reacted,
2 o while less reactive vinyl acetate has to be stripped off, and would be
recycled in
a commercial continuous process. Dialkyl maleates are considerably less
reactive.
Saponfication/hydrolysis of polyvinyl acetate) polymers and
copolymers, and isolation of the resulting PVA copolymer as a powder, is a
2 5 standard procedure, well known in the art. The PVA copolymer is typically
isolated as a granular powder.
The preferred process of this invention to prepare PVA
copolymer ionomer, is that of converting granular PVA copolymer containing
0.1 to 10 moles of a C1-C8-alkyl (meth)acrylate or CI-C3-dialkyl dimaleate or
3 0 difumarate to PVA copolymer ionomer containing from 0.1 to 10 mole percent
anionic carboxylate units. This process itself may be carried out in differing
ways. Further, after preparation, the polymer may be isolated as a solid
material
or converted directly to a size solution. While the limits of comonomer in the
ionomer and the starting PVA copolymer are the same, the amount of
3 5 ionomerization need not, and normally will not be complete. The number of
CA 02335800 2000-12-19
WO 00/01876 PCT/US99/14676
ionomer units may well be only a low percentage of the original comonomer
units in the starting copolymer. For instance if only 1 percent of comonomer
units in a PVA copolymer with 10 percent comonomer is converted to ionomer,
there will still be 0.1 percent ionomer units, which is the bottom of the
limit for
ionomer units in the ionomer for use in the sizes of this invention.
Typically,
conditions used, as described in the examples below convert an estimated 20 to
70 percent of the comonomer units to ionomer units. However, an analysis
which determines this precisely on any of the ionomers has not been carried
out.
The PVA copolymer is mixed with a liquid reaction medium and
reacted with an appropriate base, which must be somewhat soluble in the
reaction medium, for a suitable time at a suitable temperature. The reaction
medium may be chosen either to ensure that the PVA copolymer as well as the
resulting PVA copolymer ionomer remains mostly undissolved, so that the
ionomer may be readily isolated. Alternatively the reaction medium may be
chosen so that the PVA copolymer ionomer can be readily dissolved, to form a
size solution directly from the reactant mixture. With such a reaction medium.
the starting PVA copolymer is also likely to be somewhat soluble in the
medium.
The former method uses a reaction medium which is a near non-
2 0 solvent for the PVA copolymer and even less of a solvent for the PVA
copolymer ionomer formed. This process is referred to here as a slurry
process.
Specifically, the reaction medium must not dissolve more than 5 percent of
either the starting PVA copolymer, or the resultant PVA copolymer ionomer.
However, it must dissolve at least 0.001 weight percent of base material.
2 5 Reaction mediums for this slurry process include C 1-C3 aliphatic alcohols
such
as methanol, ethanol and propanol, lower alkyl ketones such as acetone, methyl
ethyl ketone, and mixtures of these with some water, to the extent the
solubility
limits are not exceeded. Methanol, and ethanol, optionally with water, are
preferred. The slurry may contain anywhere from 1 to 90 percent solids,
3 0 though 5 to 40 percent is preferred, and 10 to 30 percent most preferred.
The latter method uses a reaction medium which is a solvent for
the PVA copolymer ionomer formed, and may be a partial solvent for the
starting PVA copolymer. While it must be a solvent for the ionomer, it may be
necessary to heat the reaction product to from a solution, but it must remain
in
3 5 solution on cooling. This process is referred to here as a solution
process. In
16
CA 02335800 2000-12-19 "''""~"'
WO 00/01876 PCTNS99/14676
this case the preferred reaction medium is water, though small amounts of
lower
alcohols are allowable provided the PVA copolymer ionomer remains soluble in
it The as-formed solution may have a concentration of from 0. i to 90 weight
percent of the formed PVA copolymer ionomer in the liquid medium,
preferably from 5 to 40 percent, and most preferably from 5 to 20 percent.
In either the solution or the slurry process, the order of addition
may vary. Thus the polymer may be added to the base akeady in solution in the
reaction medium, or solid base or a solution of the base in an appropriate
solvent
may be added to the PVA copolymer/reaction medium mixture.
Suitable bases include alkali metal hydroxides, alkaline earth
metal hydroxides, and quaternary ammonium hydroxides. The preferred bases
are sodium and potassium hydroxides. The amount of the basic material
required depends on the basic material and the amount and rate of conversion
to
ionomer desired. Typically, while a stoichiometric amount, relative to the
amount of alkyl ester units desired to be converted to ionomer may be
sufficient,
more rapid reaction will occur with an excess. The amount of base may be
from 0.1 to 20 moles per 100 moles of monomer-derived units in the starting
polymer, but no more than twice the number of moles of comonomer-derived
units (or lactone units derived therefrom) in the starting polymer. For
example,
2 0 a starting polymer with 5 mole percent comonomer should employ no more
than
10 moles of base for an amount of polymer which'contains' (i.e.,has
polymerized within it) 5 moles of comonomer. For a polymer with the
maximum allowable amount of 10 moles of comonomer, 20 moles of base is the
maximum amount for an amount of polymer which contains 100 moles of
2 5 monomer and hence 10 moles of comonomer.
The rate of conversion from PVA copolymer to PVA copolymer
ionomer will be a complex function of the exact chemical nature of the PVA
copolymer, its amount in the reaction mixture, the reaction medium, the amount
and exact nature of the base used, the reaction temperature and the reaction
time.
3 o By analyzing for ionomer units formed, by IR for instance, it will be
possible to
determine suitable conditions. Typical conditions including times at what
temperature, and with which reaction medium, for different starting PVA
copolymers and conditions are shown in the Example section. These will
provide a guide for other polymers and conditions.
17
CA 02335800 2000-12-19 ., .
WO 00/01876 PCT/US99/14676
As indicated. it may be desirable after the ionomerization step,
to isolate the ionomeric PVA copolymer as a solid, since it may be convenient
to
market dry granular PVA copolymer ionomer. For sizes, fabric producers
would make their own size solutions of the PVA copolymer ionomer, or PVA
copolymer ionomer blended with other PVA copolymer, or starch. However an
endless number of possibilities exist. PVA copolymer ionomer could be
isolated as dry granular material, blended with other polymeric size
materials,
and the dry product blend shipped to fabric producers. Alternatively, the PVA
copolymer ionomer could be made into a blend size solution with other PVA
l0 polymers or starches, without ever isolating the PVA copolymer ionomer. To
prepare aqueous size solutions from granular PVA copolymer ionomer, or a
blend with other PVA polymers or starches, typically an elevated temperature
will be needed. The time and temperature required to form a solution will
depend on the actual composition, but can readily be determined by trial and
error.
Total concentration of polymer in the size solutions should be 1
to 20 weight percent, preferably 4 to 12 weight percent. The sizing solution
may
incorporate other materials typically found in sizing compositions. Such
materials may include waxy-type lubricants, defoaming surfactants, and other
2 o surfactants. A skilled artisan will be able to judge what concentration
size
solution to use to achieve his desired size add-on level, and what additives
are
best suited to his operations.
Free carboxylic acid should preferably not be present in the
polyvinyl acetate copolymers, the poly{vinyl alcohol) copolymers or in the
2 5 derived PVA ionomers, but free acid is not excluded. Small amounts of acid
may remain or be present in any of these.
Rate or ease of water solubility (which will relate to desize
sensitivity) of PVA copolymer ionomers will depend on the reduction in
crystallinity due to increasing number of comonomer units, the net decrease in
3 o polarity with increasing levels of relatively non-polar comonomer units
(usually
as lactone units) not converted to ionomer units, and the increased rate of
water
solubility due to the polar ionomer units present. Any PVA copolymer ionomer
can be expected to have a water solubility or sensitivity which is a balance
due
to the interplay of these factors. All the ester comonomers and the lactvne
ring
3 5 they can form, will be less polar and hence less water sensitive than
vinyl
18
CA 02335800 2000-12-19 -°~ 'r-°°
WO 00/01876 PCT/US99/146~fr
alcohol units but ionomer units will generally be more sensitive. The most
water sensitive PVA copolymer ionomers within the bounds of the invention
will in general be the most readily desized polymers. In some sizing
situations,
such polymers will be suitable sizes, but in others they may be too water
sensitive. However, such highly desizable compositions may be the best ones to
use in blends, since lower amounts may be needed to obtain a given level of
desizability.
Overall, PVA ionomers will have great versatility in that they can
be designed to have a varying and controllable degree of water sensitivity and
desizability based on the above factors. It will be within the skill of the
artisan,
based on trial an error, to explore the large palate of blend sizes which
blends of
this invention provide, to optimize any particular desired characteristics.
PVA homopolymers, and many non-ionomer PVA copolymers,
particularly with relatively low levels of comonomer, such as below about 6
weight percent, desize either less rapidly, or require higher temperatures for
the
same amount or ease of desizing. Caustic desizing can aid in desizing
copolymers, as has been noted. PVA copolymer ionomers, in general desize
very much more rapidly in water than the PVA copolymers from which they
derive, since they contain the highly soluble ionomer groups. Caustic desizing
2 0 also appears to aid in desizing PVA copolymer ionomers. This is
particularly
true if there are non-ionomer alkyl ester groups remaining in the copolymer,
since the copolymer is then subject to further ionomerization. One advantage
of
PVA copolymer ionomers however, is that they can be desized more rapidly,
without resorting to caustic desizing than a PVA copolymer with comparable
2 5 level of comonomer. If caustic desizing is used, caustic solutions can be
very
dilute, such as about 0.001 weight percent, particularly if somewhat elevated
temperatures are used to desize, though concentrations up to as high as 10
percent are possible.
For blends containing non-ionomeric PVA copolymers, caustic
3 0 desizing may be advantageous, though the concept of blending such
copolymers
with PVA copolymer ionomers has, as its basis, to provide an immediate
desizing advantage even in water. However, in blends which contain partially
hydrolysed PVA homopolymer, water may be favored, since any increase in
saponification due to caustic will increase crystallinity due to an increased
3 5 percent of vinyl alcohol units, and hence decrease desizability.
19
CA 02335800 2000-12-19
WO 00/01876 PCTNS99114676
Generally, excess caustic will have to be subsequently washed
off, so that higher concentration caustic than is adequate should be avoided.
For any particular PVA copolymer ionomer or blend, add-on level, fabric heat
treatment and so on, a suitable concentration for the desizing caustic
solution
and a suitable temperature for desizing can be readily determined when it has
been decided how rapidly and how completely desizing is required. Thus the
emphasis may be on the most rapid desizing for economic reasons. Or the
emphasis may be on as low temperature desizing as possible because the
material is somewhat temperature sensitive. Usually, almost complete desizing
1 o is required. There will not be just one desizing condition suitable, but a
range of
alternatives. When caustic desizing is used suitable caustic materials include
any of the alkali metal hydroxides or carbonates , i.e. sodium, potassium or
lithium, with sodium hydroxide being preferred. In some mills however,
conditions may necessitate milder desizing. When this is the case, water
desizing or desizing with carbonates can be used, and adjustments made in
concentration and time and temperature of desizing.
The yarns which can advantageously employ the sizes of this
invention are any conventi mal yarn, either from spun fiber or filament
assemblages or other weavable structures, and may be hydrophilic such as
2 o cotton or hydrophobic such as nylon or polyester or from
hydrophilic/hydrophobic combinations. Some finishing operations on (woven)
textiles or even knitted fabrics can also advantageously employ the sizes of
this
invention.
The PVA copolymer ionomers of this invention may have a 4%
2 5 solution viscosity from 1 to 60 centipoise. Preferably they should have a
viscosity between 3 and 25 centipoise . It is within the skill of the artisan
to
determine the optimum polymer viscosity, polymer size concentration, and add-
on level for the particular yarn, fabric and weaving conditions he is using.
Prior art PVA polymers in the PVA copolymer ionomer/PVA
3 o polymer blends of this invention may be any PVA homopolymer or PVA
copolymer previously known for use as size or blends of such prior art polymer
with PVA copolymer ionomer. This includes both fully and partially
hydrolysed homopolymer, and PVA copolymers with comonomer selected from
the group consisting of alkyl methacrylates, alkyl acrylates, dialkyl
fumarates
3 5 and dialkyl maleates, wherein the alkyl group contains from 1 to 8 carbon
CA 02335800 2000-12-19 .. ...
WO 00/01876 PCTNS99/14676
atoms. Partially hydrolysed non-ionomeric PVA in the blends may be from 50
to 98 % hydrolysed, but will preferably by above 80 % hydrolysed.
The starches which can advantageously have blended with them
the PVA copolymer ionomers to improve their ability to be desized (and, in
general, to improve their behavior as sizes) include natural starches,
synthetic
starches and some chemically modified starches. There are some starch derived
materials which have been so modified that they are far removed in properties
and ability to be desized, and are not particularly advantageously blended
with
the PVA copolymer ionomers. Some modified starches for instance are already
1 o fairly readily desized and/or have properties far removed from natural
starches.
Indeed such materials may already be so modified that their modification alone
may serve a similar purpose of improving sizing behavior and ability to be
desized, and blending with the PVA copolymer ionomers of the invention
provides only a modest additional advantage. Generally however, the PVA
ionomers are mare readily desized than the majority of available starches.
The starches which are blended advantageously with the PVA
copolymer ionomers of this invention are preferably natural starches or
synthetic
starches which have not been modified or have been modified to only a small
extent.
2 0 Natural starches are carbohydrates of natural vegetable origin
which are commonly considered to be composed mainly of amylose and/or
amylopectin. Specific examples of naturally-occurring starches include those
of
corn, wheat, potato, sorghum, rice, bean, cassava, sago, tapioca, bracken,
lotus,
water chestnut, and the like. These are the starches which are the preferred
size
2 5 materials of the invention because they will be substantially upgraded in
their
ability to be desized, and because in general, their properties as sizes are
poorer
than modified starches. Their main advantage is that they are relatively
inexpensive.
Examples of synthetic starches and chemically or physically
3 0 modified starches include alpha starch, fractionated amylose, moist heat
treated
starch and the like, enzymatically modified starches such as hydrolyzate
dextrin,
dextrin produced by enzymatic degradation, amylose and the like, chemical
degradation-modified starches such as acid-treated starch, hypochlorite-
oxidized
starch dialdehyde starch and the like, chemically modified starch derivatives
3 5 such as esterified starches. Specific examples of chemically-modified
starch
21
CA 02335800 2000-12-19 ,.
WO 00/01876 PCT/US99/14676
derivatives include esterified starches such as starch acetate, starch
succinate,
starch nitrate, starch phosphate, starch urea phosphate, starch xanthate,
starch
acetoacetate; etherified starches such as allyl etherified starch. methyl
etherifired
starch, carboxymethyl etherifired starch, hydroxyethyl etherified starch,
hydroxypropyl etherified starch; cationized starches such as the reaction
product
from starch and 2-diethylaminoethyl chloride, the reaction product from starch
and 2,3-epoxypropytrimethylammonium chloride; crosslinked starches such as
formaldehyde-crosslinked starch, epichlorohydrin-crosslinked starch,
phosphoric acid-crosslinked starch and the like, and any mixture of any of the
1 o above or si-nilar starches.
The blend used to prepare the size solution may contain from 10
to 90 weight percent of the PVA copolymer ionomer and from 90 to 10 weight
percent of the other PVA polymer or starch. Because of the extremely ready
desizing of ionomers containing a high level of ionomer units, the lowest
levels
will be quite effective in increasing desizability.
The PVA copolymer ionomers used in the sizes and blend sizes
of this invention may also be adaptable for uses in certain film applications.
Such films can in~:lude agricultural mulch films, biodegradable packaging
films
and water soluble films. They may also be adaptable for use as hot melt
2 o adhesives, binders and the like.
EXAMPLES
The PVA copolymer ionomer listed in Table 1 as C9AI, is an
example of the 'slurry' method of preparation of PVA copolymer ionomer from
PVA copolymer. a was prepared as follows: SO grams of PVA polymer C9A
was added to a solution of 0.64 g. of sodium hydroxide in 30 grams of water
and
120 grams of methanol, with stirring, to form a slurry. The slurry was stirred
at
room temperature, about 22°C, for 1 hour arid then vacuum filtered
through a
fritted glass filter. The wet filtrate was dried in a vacuum oven under
nitrogen,
3 0 at room temperature, then overnight for about 4 hours at 80°C.
White granular
product (about 49.6 grams) was obtained. The amount of sodium hydroxide
used is sufficient to ionomerize about one third of the comonomer units. The
polymer had 9 weight percent comonomer or about 6 mole percent. Thus the
product has about 2 mole percent ionomer units.
3 5 To make a size solution from this, it is only required to dissolve
22
CA 02335800 2000-12-19 ~w°
WO 00/01876 PCT/US99/14676
in water at a temperature sufficient to enable it to dissolve in a reasonable
time.
Generally, 2 hours at about 90°C will be more than adequate. Blend
sizes
which included this slurry PVA copolymer ionomer were made by dissolving
50/50 mixtures of this polymer and the other blend component together in water
for 2h. at 90°C. This polymer was used extensively in desizing tests,
and was
the only slurry polymer so tested. Other slurry process PVA copolymers
ionomers were prepared using the same method, but using different starting
polymers and different amounts of base. The same process was also carried out
on polymers not capable of forming ionomers, as controls, so the polymers
1 o could be compared. The polymers used, the amount of base used, and certain
properties of the polymers are listed in Table IV. The above example of slurry
ionomerization is included in the table (C9A polymer with 0.64 g NaOH). The
properties are designed to illustrate the extent of ionomerization based on IR
testing, and the effect this has, for different starting polymers, on
solubility and
solubility rate.
The'solution' process to make PVA copolymer ionomers, i.e.,
where the reaction medium is essentially water, so that the polymer can be
dissolved in the reaction medium, is illustrated by the following example. A
weight of 0.13 grams of sodium hydroxide was dissolved in 45 grams of water,
2 o and 5 grams of polymer C9A was added and stirred for S minutes at room
temperature. The mix was then heated to 90°C and kept at this
temperature for
one hour. The resulting solution was clear. Table IV shows IR analysis and
Filrn dissolution times for several PVA copolymer ionomers prepared in this
way, as well as polymers not capable of forming ionomers, but treated in the
2 5 same way.
Analytical tests were as follows:
Warm Water Solubles. All PVA polymers are soluble in water if
the water is heated sufficiently. In order to differentiate water solubility
of
different materials, solubility w:.s determined under a chosen set of
intermediate
3 o temperature conditions. The conditions are: 35 °C for 1 hour. The
test was
only used for slurry polymer, since the slurry process produces solid granular
polymer, whereas the solution process results in polymer solutions.
23
CA 02335800 2000-12-19 ~;,
WO 00/01876 PCT/US99/14676
grams of polymer is slurried with 190 grams of water at 35 °C
for 1 hour with gently mixing. After cooling, the remaining solids were
filtered
off, and an aliquot of clear filtrate dried in an aluminum pan in a dessicator
box
and the weight of polymer in the aliquot determined. Percent solubles could
5 then be calculated. Results are shown in Table IV.
Infra-red Analysis was determined on cast films. For slurry
polymers, 10 percent solutions were prepared by dissolving at 80°C for
1 hour.
Solution process prepared polymers were used directly for casting. Films were
cast using a 1 ~ mil knife gap at 52°C, allowed to dry for 30 minutes,
and further
1 o dried in a vacuum over, overnight at room temperature under nitrogen, then
at
80°C for 4 hours. Stripped films were stored in a desiccated box.
IR analysis was performed on the films using a Nicolet 710 FT-
IR spectrometer. The IR peak at 1725-1750 cm-l, according to known art, is
due to lactone function, i.e., the result of internal lactonization of the
methyl
acrylate or methyl methacrylate comonomer with hydroxyl of the vinyl alcohol.
Its presence can be considered to indicate non-ionomerized units, either
because
conditions (e.g. control conditions of no base) could not ionomerize, or
because
incomplf to conversion of lactone to ionomer units occt;rred. No attempt was
made to quantify the amount of remaining lactone units. Result are expressed
2 o qualitatively. The IR peak at 1550-1575 cm-1 is, based on the art,
attributed to
the carboxylate ionomer units. The presence of small amounts of sodium
acetate ash however will also cause a peak at this wave number, so that all
samples, even without any ionomer units show small peaks in this region.
Results are shown in Table IV.
Film Dissolution Time. A further test of water solubility was
carried out; in this instance time to dissolve at ambient temperatures, rather
than
amount soluble under specific temperature/time conditions. Films prepared as
above were suspended in water with gentle stirring, and the time for complete
dissolution was determined. Results are shown in Table IV.
24
CA 02335800 2000-12-19
WO 00/01876 PCT/US99114676
All three tests give an indication of the amount of ionomerization
of any of the three copolymers tested. For polymer C3M it can be seen that the
35°C solubles increases dramatically on ionomerization with 0.84 grams
of base
in 200 grams of reaction medium, from 6.7 percent for non-ionomerized
copolymer to 34.4 percent after ionomerization. Dissolution time decreases
from 25.3 to 8.5 minutes, and the ionomer IR peak at 1550-1570 cm-1 increases
at the expense of the lactone IR peak at 1725-1750 cm-1. As the amount of
base is decreased for C3M, it is seen the 35°C solubles decreases,
indicating less
of the alkyl methacrylate units have been ionomerized. Similar trends are
observed for polymers CSM and C9A, though an occasional result appears to be
off trend, as for example the 35°C solubles for ionomerized C9A using
slurry
polymerization appears to be less for 2.56 grams of base than for 1.28 grams
of
base. Both values however are very high compared with non-ionomerized C9A
control. Generally, C9A non-ionomerized copolymer is more soluble than
C3M and CSM in these tests, and the ionomers derived from it are relatively
more soluble than similar ionomers derived from the C3M and CSM polymers.
Similar trends are seen for solution polymers.
PVA copolymer ionomers used in desizing tests were all
prepared by the solution process, except for C9AI. The solution process was
2 0 used because the result of the process is a solution ready to use as a
size. While
the process was in essence, always the same, minor differences, in terms of
whether base was added as solid or aqueous solution to polymer/liquid medium
mixture (loosely a slurry, but not to be confused with the slurry process
where
the final polymer is always in the form of a slurry rather than a solution) or
2 5 whether polymer was added to base solution, etc. were made. Table II lists
the
polymers used, and details of the solution process used with regard to the
above
minor differences are shown. When blend sizes were prepared, the blend
component not capable of being ionomerized was mixed with the ionomerizable
polymer at ambient temperatures in the reaction medium (water, as distinct
from
3 o methanol/water mixtures used in the slurry process), and both polymers
were
then heated to 90°C, principally to complete dissolution, but also to
further
ionomerize the ionomerizable polymer.
CA 02335800 2000-12-19 ,~,,"
WO 00/01876 PCT/US99/14676
Size solutions were generally clear and slightly viscous if only
PVA polymers were used. When starches were part of the blends, some
haziness was sometimes present, the starch being suspended rather than fully
dissolved.
When blend sizes were tested, the blends contained 50 weight
percent of each component. Sizes tested are listed in Table II which is
divided
into three sections. The first section, Table IIA lists sizes based on a
single
polymer. The second section, Table IIB is for sizes based on blends of PVA
copolymers, some controls and some ionomer blends. The third section, Table
IIC is for starch/PVA copolymer or ionomer blends.
Sized fabric samples were prepared as follows. Approximately 2
inch by 2 inch squzres of a ? o»nce, all cotton, bleached, duck fabric type
464
obtained from Test Fabrics Inc. were first weighed, then soaked in size
solution
for about 2 minutes at about 35 deg. C., mixing gently. Fabric weight was
generally between 0.4 and 0.7 grams, and the amount of size added on between
about 0.13 and 0.4 grams. The samples were then dried by placing on aluminum
foil, treated with Teflon lubricant to prevent sticking, at 50 deg. C. in a
;onvection oven far 17 +/- 1 hours. They were then cooled in a calcium sulfate
desiccated box, and reweighed to determine the amount of size added on. In
2 o some cases the samples were heat-treated by placing in a convection oven
at 140
deg. C. for 10 minutes.
Desizing tests were carried out by soaking the sized fabric sample
in 100 grams of the test desizing medium, (either water or caustic) for 10
minutes with gentle mixing. In some instances when water was used, the
2 5 sample was further desized by soaking in another 100 grams of water for 10
minutes. In all instances when caustic was used, the sample was subsequently
soaked in 100 grar~ms of water for 10 minutes. This subsequent water treatment
washes out the caustic as well as providing for slight further desizing. The
desizsd or partially desized samples were then dried in a convection air oven
at
3 0 140 deg. C. for 1 hour and then allowed to cool in a calcium sulfate
desiccated
box. Details, are shown in the Tables III which is divided into three
sections.
The first section, Table IIIA is for single polymer compositions (ionomers and
controls), the second, Table IIIB for mixed PVA polymer compositions
(ionomer and non-ionomer blends) and the third. Table IIIC for mixed PVA
3 5 copolymer/starch compositions (the copolymer being either ionomer or non-
26
CA 02335800 2000-12-19 d",..,,"",
WO 00/01876 PCTNS99/14676
ionomer. T_ he sizing tests in each of the Table III tables employs a size
listed in
the corresponding Table II. (e.g.,. Table IIIB and Table IIB).
When examples of PVA copolymer ionomer or blend sizes of the
invention are shown in the tables, they are given a number without a prefix C.
When examples of sizes outside the compositions of the invention are listed,
whether from a single non-ionomer PVA polymer or from a blend which does
not include PVA copolymer ionomer of the invention, they are labeled with a
prefix C, indicating they are shown for comparison.
While complete desizing is generally considered necessary, the
1 o percent desizing in the examples is considered to be an indication of the
ease of
complete desizing. If the value shown is less than 100%, then longer desizing
times, different caustic concentration or somewhat higher temperatures would
be
necessary to achieve complete desizing. Double washes (i.e. equivalent to
longer desizing times) produced increased desizing.
In some examples the sized fabrics were heat treated, and some
were subjected to a double water wash. Heat treating can in some instances
decrease desizability, particularly in compositions which contain a high
portion
of partially hydrolysed PVA polymer, particularly homopolymer.
Desizing times are deliberately short, in order to make
2 0 comparisons of ease of desizing. Amount of desizing is listed as
'Apparent'
percent size removed. This is because minor amounts of other material from the
fabric is removed in desizing tests, in addition to the size, so that some
values
are seen to be slightly greater than 100 percent. Longer times would
completely
desize most samples.
2 5 Examples 1, 2, 3, 5 and 10 show the ease of water desizing of
non-ionomer PVA polymers. Partially hydrolysed homopolymer is most easily
removed of these and fully hydrolysed homopolymer the least. The other three
examples are for copolymers with two different levels of methyl methacrylate,
and one with a high level of methyl acrylate. Examples 6 and 9 illustrate the
3 o effect of increasing levels of ionomerization of polymer CSM. (Example 5
is for
non-ionomerized CSM). The ionomers are more readily desized and the more
highly ionomerized composition is more readily desized. Example 7 shows that
for longer desizing times (twice desized), more desizing occurs, indicating
complete desizing will occur with long enough desizing time. Example 8 shows
3 5 that dilute base produces higher desize levels for the same polymer, CSM.
This
27
CA 02335800 2000-12-19
WO 00/01876 PCTNS99/14676
suggests that the ionomerized polymer of size SZ6 can be further ionomerized
with base. Examples I l and 12 are for ionomerized polymer C9A. Example 12
shows that an increase in desizing temperature increases the amount of
desizing
for ionomers. Example 15 shows that even ionomers are less readily desized
after heat treatment (compare Pxample I3), but that higher desize temperatures
once again allow complete desizing.
Generally. ionomers produced from PVA copolymers with a
higher level of comonomer are more readily desized, and the greater the amount
of ionomerization of that PVA copolymer, the greater ease of desizing. While
there are non-ionomer materials which are more readily desized than some of
the ionomers which have been prepared to have lower ionomer levels (i.e., from
low comonomer PVA copolymers, and/or using low levels of base), ionomers
provide a ready alternative to such non-ionomer PVA polymers or copolymers.
An ionomer will require less comonomer in the PVA starting polymer for a
given ease of desizing, which in many cases will be an advantage from a
preparative ease of polymerization, as well as from a cost point of view. In
this
sense, considerably fewer ionomer units are required than non-ionomer
comonomer units to allow a given ease of desizing.
The next two tables show an extensive list of blend sizes. The
2 o first with other PVA polymers; and the second with starches. Close
examination
of the ease of desizing will be seen to show that ease of desizing is, very
roughly, a weighted mean of the ease of desizing of components. It follows
that
when a highly ionomerized high comonomer copolymer ionomer is used in
blends, it will very effectively increase ease of desizing. As a single
example,
size SZ40BS-C and size SZ41BS are C9A/Starch S4 blends. The control blends
is a non-ionomer blend, while SZ41BS blend has been subjected to
ionomerization conditions, and thus the C9A component has been ionomerized.
The amount desized (examples 51 and 52), increases from 54.8 percent to 94.1
percent. Other examples generally follow a similar pattern.
28
CA 02335800 2000-12-19 ..r ~;,,,",
WO 00/01876 PCT/US99/t4676
TABLE L: PVA SAMPLES TESTED
Code Solution Mole Composition Description
%
Viscosi Hydrolysis
H88-I21-26 8?-89 Partially hydrolysed'homopolymer'
H88-244-50 87-89 Partially hydrolysed'homopolymer'
H99-I12-I S 99-99.8 'Fully' hydrolysed homopolymer
H99-227-33 99-99.8 'Fully' hydrolysed homopolymer
C3M 24-32 99-99.8 Fully hydrolysed copolymer 1.9
mole % (~3 wt
%) MMA
CSM 12-I 5 98 - 99.8 Fully hydrolysed copolymer 2.8
mole % (~S wt
MMA
C9A 1 S-21 98-99.8 Fully hydrolysed copolymer b.0
mole % (~9 wt
MA..
C9AI nm 98-99.8 Partially Ionomerized C9A (~30%
of
Comonomer units
S - - Natural Cornstarch : CAS 68412-30-6
1
S2 - - Chemically modified Starch:
hydroxyethyl
starch ether, CAS 9005-26-0
S3 - - Chemically modified Starch:
oxidized
carboxymethyl starch ether CAS
9063-38-1
S4 - - Chemicall modifed Corntarch:
ethyoxylated
starch ether, CAS 68512-26-5
Polymer code designations summarize the nature of the composition; H for
Homopolymer, C for Copolymer 88 for ~88 mole % hydrolysed, M for methyl
methacrylate comonomer, and A for methyl acrylate comonomer.
Solution Viscosity in Centipoise, measured on a 4 weight percent solution at
20
1 o deg.C., determined by Hoeppler falling ball method, bond dry basis.
All samples have a solution pH between S and 7. All samples have a maximum
ash level of 0.7 weight percent calculated as sodium oxide, dry basis.
Comonomer level in copolymer is listed in weight percent, calculated as non-
lactonized comonomer unit in the polyvinyl alcohol) chain and in Mole percent.
Codes C3M, CSM, C9A: number refers to weight percent comonomer.
C9AI = Ionomerized C9A.
Comonomer abbreviations: MMA= methyl methacrylate; MA = methyl acrylate
2 0 S 1 Tradename: Clinl-link 692B, ADM Corn Processing Co., Clinton Iowa.
S2 Tradename: Penford Gum 260, Penford Products Co.,Cedar Rapids, Iowa.
S3 Tradename: Astrogum 3010, Penford Products Co.
S4 Tradename: Clinton 712D, ADM Corn Processing Co.
29
CA 02335800 2000-12-19
WO 00/01876 PCT/US99/14676
TABLE IIA
COMPOSITION OF SIZES TESTED
Size Composition
SZ1-C 8% H88-1 in water
Polym>water/90C/2h.
SZ2-C 8% H99-1 in water
Polym.>water/90C/2h.
SZ3-C 8% G3M in water
Polym>water/90C/2h
SZ4 8% C3M in 0.1% NaOH
Polvm>soln/90C/2h.
SZS-C 8% CSM in water
Polym>water/90C/2h.
SZ6 8% CSM in 0.1% NaOH
Polym>soln/90C/2h.
SZ7 8% CSM in G.2% NaOH:
Solid NaOH>RT Poly.slurry
+ 90C/2h.
SZ8-C 8% C9A in water
Polym>water/90C/2h.
SZ9 8% C9A in 0.045 NaOH
NaOH soln>RT Poly.slutry
+ 90C/2h.
SZ10 8% C9A in 0.1% NaOH
Polym>soln./90C/2h.
SZ11 8% C9AI in water
Polym>water/90 C/2h.
SZ12 8% C9A-in 0.22% NaOH
Solid NaOH>RT Poly.slurry
+ 90C/2h.
SZ13 8% C9A in 0.45% NaOH
Polym>soln/90C/2h.
SZ I 8% C9A in 0.1 % KOH
4
Solid KOH>RT Poly.slurry
+ 90C/2h.
30
CA 02335800 2000-12-19 ..,::,w,;
WO 00/01876 PCTNS99/14676
TABLE IIB
PVA BLEND SIZE COMPOSITIONS
Size Composition
SZ15BP-C 8% 1/1 H99-1/C3M in water
Polym>water/90C/2h
SZ16BP 8% Ill H99-1/C3M in 0.025% NaOH
C3M>soln@RT + H99-1 + 90CI2h.
SZ17BP-C 8% I/1 H88-1/C5M in water
Polym.>water/90/2h.
SZ18BP 8% l/1 H88-1/C5M in .025% NaOH
CSM>soln@RT + H88-I + 90C/2h.
SZ19BP 8% 1/1 H99-l/C5M in 0.048% NaOH
Solid NaOH>RT C5M slurry +H99-1
+ 90C/2h.
SZ20BP-C 8% 1/1 C5M/C9A in water
Polym.>water90/2h.
SZ21BP 8% 111 C5M/C9A in 0.02%NaOH
Solid NaOH>CyA slurry +C5M +90C/2h.
SZ22BP-C 8% I /1 H99-1 /C9A in water
Polym>water/ 90C/2h.
SZ23BP 8% 1/1 H99-1IC9A in 0.05% NaOH
C9A>soln.RT + H99-1 +90C/2h.
SZ24BP-C 8% III H88-1/C9A in water
Polym>water/90C/2h.
SZ25BP 8% I/1 H88-1/C9A in 0.05% NaOH
C9A>soln +H88-1 + 90C/2h.
SZ26BP-C 8% 1 / 1 H99-2/C9A in water
Poiym.>water/ 90C/2h.
SZ27BP 8% 1 / 1 H99-2/C9AI in water/
90Cl2h.
SZ28BP 8% 1!1 H99-1/C9A in 0.45% NaOH
Solid NaOH>H99-1/C9A slurry mix
+ 90C/2h.
31
CA 02335800 2000-12-19.".
WO 00101876 PCTNS99/14676
TABLE IIB - contd
PVA BLEND SIZE COMPOSITIONS
Size Composition
SZ29BP-C 8% 1/1 H88-2/C9A in water
Polym.>/90°C/2h.
SZ30BP 8% 1/1 H88-2/C9A in 0.22% NaOH
C9A>soln + I-I88-2 + 90°C/2h.
SZ31BP-C 8% 1/1 C3M/C9A in water
Polym>water/90°C/2h.
SZ32BP 8% 1/1 C3M/C9A in 0.025% KOH
Solid KOH>C9A slurry + C3M + 90°C/2h.
32
CA 02335800 2000-12-19 ...,..
WO 00!01876 PCTNS99/14b7b
TABLE IIC
PVA/STARCH SIZE COMPOSITIONS
Size Composition
SZ33BS-C 8% 1/1 S1/C3M in water
Polym.>water/90C/2h.
SZ34 8% 1/I S 1/C3M in 0.05% NaOH
C3M>soln + S I + 90C/2h.
SZ35BS-C 8% I /I S2/CSM in water
Polym>water/90C/2h.
SZ36BS 8% 1/1 S2/CSM in 0.05% NaOH
CSM>soln + S2 + 90C/2h.
SZ37BS 8% I /I S 1/CSM in 0.1 % NaOH
Solid NaOH>CSM slurry + S 1
+ 90C/2h.
SZ38BS-C 8% 1/I S3/C9A in water/90C/2h.
SZ39BS 8% 1/1 S3/C9A in 0.023% NaOH
NaOH soln>C9A slurry +S3 +90C/2h.
SZ40BS-C 8% 1/1 S4/C9A in water
Polym>water/90C/2h.
SZ41BS 8% 1/I S4/C9A in 0.05%NaOH
C9A>soln + S4 + 90 C/2h.
SZ42BS-C 8% 1 / 1 S 1 /C9A in water
Polym>water/90C/2h.
SZ43BS 8% I / I S 1 /C9A in 0.05%
NaOH
C9A>soln + S I + 90C/2h.
SZ44BS-C 8% 1/1 S2/C9A m water/90C/2h.
SZ45BS 8% 1/I S2/C9A in 0.05% NaOH
C9A>soln + S2 + 90C/2h.
33
CA 02335800 2000-12-19
WO 00/01876 PCTNS99/14676
TABLE IIC - contd.
PVA/STARCH SIZE COMPOSITIONS
Size Composition
SZ46BS 8% 1/1 S3/C9AI in water
Polym.>water/90°C/2h.
SZ47BS 8% 1/1 S4/C9A in 0.11% NaOH
Solid NaOH>C9A slurry + S4 + 90°C/2h.
SZ48BS 8% 111 S3/C9A in 0.23% NaOH
C9A >soln + S3 + 90°C/2h.
SZ49BS 8% 1/1 S2/C9A in 0.05% KOH
Solid KOH>C9A slurry + S2 + 90°C/2h.
34
CA 02335800 2000-12-19 . ~_"""",",
WO 00/01876 PCTNS99/1467ir
Explanation of Process Steps:
First line in last cell in row states the overall composition;
Second line explains process steps and their order
Examples:
Solid NaOH >RT Poly.slurry + 90°C/2h.: Solid sodium hydroxide was
added
to (>) a slurry of polymer at Room Temperature, followed by (+) heating at
90°C for 2 hours.
Polym > soln./90°C/2h. : Polymer added to(>) base solution, followed
by (+)
heating to 90°C for 2 hours.
Poly > water: Polymer added to water..
8% 1/1 S1/CSM in 0.1% NaOH: Composition is an 8% solution of a 1/1 mix of
starch S1 and polymer CSM prepared using a base concentration of 0.1 % by
weight.
Solid NaOH >CSM slurry + S1 + 90°C/2h.: The process steps were to
add solid
sodium hydroxide to a slurry of CSM polymer, then add starch S 1, then heat to
90°C for 2 hours.
CA 02335800 2000-12-19
.. xz.~e
WO 00/01876 PCT/US99/14676
TABLE IIIA
DESIZING
TESTS
EX Size Heat Desize Desize Apparent
#
Treatment T_emt~ % Size
Medium C
R emoved
1 SZ 1-C N W 23 65.5
2 SZ2-C N W 22 27.5
3 SZ3-C N W 22 29.7
4 SZ4 N W 22 44.2
SZ5-C N W 22 51.9
6 SZ6 N W 22 75.7
7 SZ6 N W/W 22 88.7
8 SZ6 N 0.1 %NaOH 22 96.4
9 SZ7 N W 22 99.5
SZ8-C N W 23 36.6
11 SZ9 N W 23 55.6
12 SZ9 N W 50 93.4
13 SZ 10 N W 22 82.2
14 SZ10 N W 50 100.5
SZ10 Y W 22 45
16 SZ10 Y W 50 100.4
1 SZ 11 N W 22 92.9
~
18 SZ12 N W 23 87.9
19 SZ12 N W 50 103
SZ13 N W 23 105.2
21 SZ 14 N W 22 77.2
36
CA 02335800 2000-12-19 ,.;:.,:::~,:..
WO 00/0187b PCT/US99/14676
TABLE IIIB
DESIZING TESTS - contd.
EX ~ Heat Desize Desize Apparent
#
TreatmentMedium Temn % Size
C
Removed
22 SZ15BP-C I~T W 22 27.0
23 SZIbBP N W 22 33.4
24 SZ 17BP-CN W 22 62.8
25 SZ18BP N W 22 63.2
26 SZ18BP N W 50 96
27 SZ19BP N W 22 51.7
28 SZ20BP-C N W 22 45.8
29 SZ21BP N W 22 74.6
30 SZ21BP N W/W 22 91.1
31 SZ22BP-C N W 22 43.4
32 SZ23BP N W 22 51.1
33 SZ23BP N W 50 90.7
34 SZ24BP-C N W 22 60.6
35 SZ25BP N W 22 81.7
36 SZ25BP N 0.1%NaOH 22 103.1
37 SZ26BP-C N W 22 29.8
38 SZ27BP N W 22 45.6
39 SZ28BP N W 22 56.3
40 SZ29BP-C N W 22 49.3
41 SZ30BP N W 22 77.7
41 SZ31 N W 22 32.2
43 SZ32 N W 22 54.2
37
CA 02335800 2000-12-19
WO 00/01876 PCTNS99/14676
TABLE IIIC
DESIZING TESTS - contd
EX Size Heat Desize Desize Apparent
#
TreatmentMedium Temp % Size
C
Removed
44 SZ33BS-C N W 22 38.5
45 SZ34BS N W 22 86.8
46 SZ35BS-C N W 22 48.2
47 SZ36BS N W 22 80.2
48 SZ37BS N W 22 100.2
49 SZ38BS-C N W 22 55.6
50 SZ39BS N W 22 82.8
51 SZ40BS-C N W 22 54.8
52 SZ41BS N W 22 94.1
53 SZ42BS-C N W 22 35.9
54 SZ43BS N W 22 96.1
55 SZ44BS-C N W 22 35.8
56 SZ45BS N W 22 82.5
57 SZ46BS N W 22 84.0
58 SZ47BS N W 22 89.7
59 SZ48BS N W 22 70.0
60 SZ48BS N W 50 101.6
61 SZ48BS Y 0.1%NaOH 22 99.2
62 SZ49BS N W 22 64.9
W= Water desizing. W/W = Twice desized
38
CA 02335800 2000-12-19 ~ ~;;;"",,
WO 00/01876 PCTNS99114676
TABLE IV
PROPERTIES OF PVA POLYMERS SUBJECTED TO IONOMERIZATION
CONDITIONS
NaOH PolymerSl~ 35C : DissolutionIR cm-I IR m-1
grams or %SolublesTime/ 1725-50 1550-75
C
Solution
0 C3M slurry 6.7 25.3 / ++++ +
18.7
0.84 C3M " 34.4 8.5 / +++ +++
18.7
0.63 C3M " 19.9 nm nm nm
0.42 C3M " 7.2 nm nm nm
0 CSM " 6.2 3.8 /22.8++++ +
1.21 CSM " 84.0 5.1 I +++ +++
21
0.91 CSM " 54.5 nm nm nm
0.61 CSM " 23.9 2.5 / +++ ++
21
0.30 CSM " 11.8 nm nm nm
0 C9A " 8.15 2.8 / +++-~ +
22.3
2.56 C9A " 60.34 0.8 / ++ +++
18.1
1.28 C9A " 88.2 nm nm nm
0.64 C9A " 62.0 nm nm nm
0.16 C9A " 24.6 2.0 / ++++ ++
19.8
0 C3M solutionnm 60 /21.7 nm nm
0.08 C3M " nm 7.9 /21/7+ ++++
0 C9A " nm 1.8/ 20.9+~-E++ +
0.13 C9A " nm 0.9 /20.50 +++++
run - not measured
+++++ largest peak, ++++- very large peak, +++ large peak, ++ moderate peak,
+ small peak
39
