U.S. patent application number 10/716930 was filed with the patent office on 2004-06-17 for novel fluorinated and alkylated dibenzylidene alditol derivatives.
Invention is credited to Anderson, John D., Mehl, Nathan A..
Application Number | 20040116515 10/716930 |
Document ID | / |
Family ID | 27096622 |
Filed Date | 2004-06-17 |
United States Patent
Application |
20040116515 |
Kind Code |
A1 |
Anderson, John D. ; et
al. |
June 17, 2004 |
Novel fluorinated and alkylated dibenzylidene alditol
derivatives
Abstract
Plastic additives which are useful as nucleating agents and
which are especially useful for improving the optical properties of
polymeric materials are provided. More particularly, this invention
relates to certain alkyl (or alkoxy) substituted fluoro-benzylidene
sorbitol acetals and polymer compositions thereof which may be
utilized within, as merely examples, food or cosmetic containers
and packaging. These inventive fluorinated and alkylated
benzylidene sorbitol acetals are also useful as gelling agents for
water and organic solvents, particularly those used in the
preparation of antiperspirant gel sticks.
Inventors: |
Anderson, John D.; (Moore,
SC) ; Mehl, Nathan A.; (Moore, SC) |
Correspondence
Address: |
William S. Parks
P.O. Box 1927
Spartanburg
SC
29304
US
|
Family ID: |
27096622 |
Appl. No.: |
10/716930 |
Filed: |
November 19, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10716930 |
Nov 19, 2003 |
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10243247 |
Sep 13, 2002 |
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10243247 |
Sep 13, 2002 |
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09816965 |
Mar 23, 2001 |
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09816965 |
Mar 23, 2001 |
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09653935 |
Sep 1, 2000 |
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6300525 |
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Current U.S.
Class: |
514/464 ;
549/443 |
Current CPC
Class: |
A61Q 15/00 20130101;
C07C 45/49 20130101; C07D 319/06 20130101; C07D 493/04 20130101;
C08L 23/00 20130101; C07C 47/55 20130101; C07C 45/49 20130101; C08K
5/1575 20130101; C08K 5/1575 20130101; C07C 47/55 20130101; A61K
8/042 20130101; A61K 8/498 20130101 |
Class at
Publication: |
514/464 ;
549/443 |
International
Class: |
C07D 317/44 |
Claims
What is claimed is:
1. A benzylidene alditol acetal comprising at least one substituted
benzylidene component wherein said at least one substituted
benzylidene component possesses at least one fluorine pendant group
and at least one other pendant group, wherein said at least one
other pendant group is not hydrogen, and wherein if said at least
one other pendant group is fluorine, at least one other
non-hydrogen pendant group is present on said benzylidene
component.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of co-pending application
Ser. No. 10/243,247, which is a continuation of co-pending
application Ser. No. 09/816,965, which is a continuation-in-part of
application Ser. No. 09/653,935, now U.S. Pat. No. 6,300,525.
FIELD OF THE INVENTION
[0002] This invention relates to plastic additives which are useful
as nucleating agents and which are especially useful for improving
the optical properties of polymeric materials. More particularly,
this invention relates to certain alkyl (or alkoxy) substituted
fluoro-benzylidene sorbitol acetals and polymer compositions
thereof which may be utilized within, as merely examples, food or
cosmetic containers and packaging. These inventive fluorinated and
alkylated benzylidene sorbitol acetals are also useful as gelling
agents for water and organic solvents, particularly those used in
the preparation of antiperspirant gel sticks.
BACKGROUND OF THE PRIOR ART
[0003] All U.S. Patents cited below are herein entirely
incorporated by reference.
[0004] Numerous attempts have been made to improve the clarity and
physical properties of polyolefins through the incorporation of
certain kinds of additives. Certain applications require good
clarity or transparency characteristics. These include certain
types of plastic plates, sheets, films, containers, and syringes
that need to exhibit clarity primarily to facilitate identification
of articles, etc., stored, wrapped, and/or covered therewith. Such
commercially available plastic additives fall into two categories
termed "melt sensitive" and "melt insensitive". Melt sensitive
additives possess melting points below or near the normal
processing temperatures of polyolefin-based resins and include
dibenzylidene sorbitol (DBS) systems. Melt insensitive additives do
not melt at normal processing temperatures and include sodium
benzoate and salts of organic phosphates as examples.
[0005] U.S. Pat. No 4,016,118 to Hamada, et al. teaches that a
polyolefin plastic composition containing 0.1% to 0.7%
dibenzylidene sorbitol (DBS) as an additive will show improved
transparency and reduced molding shrinkage over compositions
containing a substituted benzoic acid salt. Additional advancements
in sorbitol-based clarification technology have been driven by the
need for improved transparency, reduction of plate-out during
processing, and improved organoleptic properties (e.g., odor,
taste, etc.). In order to overcome these deficiencies, many
derivatives of DBS in which the aromatic rings are substituted with
various groups have been proposed.
[0006] Mahaffey, in U.S. Pat. No. 4,371,645 discloses a series of
dibenzylidene sorbitols having the general formula: 1
[0007] wherein R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4, are
selected from hydrogen, lower alkyl, hydroxy, methoxy, mono- and
di-alkylamino, amino, nitro, and halogen, with the proviso that at
least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is chlorine or
bromine. Effective concentrations of the disclosed substituted DBS
derivatives range from 0.01 to about 2 percent of the total
composition by weight. Further improvements in transparency
characteristics are disclosed by Titus, et al. in U.S. Pat. No.
4,808,650. In this patent mono and disubstituted DBS derivatives
having the formula: 2
[0008] in which R may be hydrogen or fluorine provide improved
clarity applications in polyolefins. Rekers, in U.S. Pat. No.
5,049,605 discloses a series of dibenzylidene sorbitols having the
general formula: 3
[0009] in which R.sub.1 and R.sub.2 are independently selected from
lower alkyl groups containing 1-4 carbons which together form a
carbocyclic ring containing up to 5 carbon atoms. Also disclosed
are polyolefin plastics containing the above group of dibenzylidene
sorbitols. Videau, in U.S. Pat. No. 5,696,186 discloses substituted
DBS derivatives with an alkyl group (methyl, ethyl, or the like) or
halogen (fluorine, chlorine, or the like) on the benzene rings for
use as nucleation/clarification agents in polyolefins.
[0010] Dibenzylidene sorbitol (DBS) is a well known gelling agent
for a variety solvent systems as disclosed in U.S. Pat. No.
4,154,816, Roehl et al.; U.S. Pat. No. 4,816,261, Luebbe et al.;
and U.S. Pat. No. 4,743,444 to McCall. U.S. Pat. No. 5,609,855 to
Oh et al. and PCT Patent Application WO/92/19221 to Juneja et al.;
disclose that di(meta-fluorobenzylidene) sorbitol and
di(meta-chlorobenzylidene) sorbitol are extremely useful as gelling
agents in the preparation of antiperspirant gel sticks. These two
respective DBS systems form effective hard gels and show improved
gel stability in the acidic environment of antiperspirant
formulations.
DETAILED DESCRIPTION OF THE INVENTION
[0011] According to the present invention, a polyolefin plastic
composition having improved transparency is provided which
comprises a polymer selected from aliphatic polyolefins and
copolymers containing at least one aliphatic olefin and one or more
ethylenically unsaturated comonomers and at least one di-acetal of
an alditol (such as sorbitol, xylitol, and ribitol), said di-acetal
of the alditol having the structure: 4
[0012] wherein R is independently selected from hydrogen, lower
alkyl groups containing 1-4 carbon atoms, lower alkoxy groups, and
fluorine; R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from
lower alkyl groups containing 1-4 carbon atoms, lower alkoxy
groups, chlorine, and fluorine; with the proviso that one and only
one of R.sub.1 and R.sub.2 is fluorine and one and only one of
R.sub.3 and R.sub.4 is fluorine.
[0013] This invention also encompasses such specific compounds
themselves, in their broadest sense defined as benzylidene alditol
acetals comprising at least one substituted benzylidene component
wherein said at least one substituted benzylidene component
possesses at least one fluorine pendant group and at least one
other pendant group, wherein said at least one other pendant group
is not hydrogen, and wherein if said at least one other pendant
group is fluorine, at least one other non-hydrogen pendant group is
present on said benzylidene component. Furthermore, a composition
of the same type of thermoplastic comprising at least one
mono-acetal alditol of the structure: 5
[0014] wherein R is independently selected from hydrogen, lower
alkyl groups containing 1-4 carbon atoms, lower alkoxy groups,
chlorine, and fluorine; R.sub.1 and R.sub.2 are selected from lower
alkyl groups containing 1-4 carbon atoms, lower alkoxy groups,
chlorine, and fluorine; with the proviso that one and only one of
R.sub.1 and R.sub.2 is fluorine. Such monoacetal compounds are also
encompassed within this invention.
[0015] It should be appreciated with regard to the structural
formula set forth above that while only the 1,3:2,4 isomer is
represented, this structure is provided for convenience only and
the invention is not limited to only isomers of the 1,3:2,4 type,
but may include any and all other isomers as well so long as the
compound contains two aldehyde substitutents on the alditol
moiety.
[0016] The diacetals and monoacetals of the present invention are
condensation products of alditol, such as sorbitol or xylitol, and
a fluoro-alkyl substituted benzaldehyde. Examples of suitable
substituted benzaldehydes include 4-fluoro-3-methylbenzaldehyde,
3-fluoro-4-methylbenzaldehyde, 4-fluoro-2,3-dimethylbenzaldehyde,
3-fluoro-2,4-dimethylbenzaldehyde,
2,4-difluoro-3-methylbenzaldehyde,
4-fluoro-3,5-dimethylbenzaldehyde, and
3-fluoro-4-methoxybenzaldehyde. Preferred di-acetals of the present
invention include bis(4-fluoro-3-methylbenzylidene) sorbitol and
bis(3-fluoro-4-methylbenzy- lidene) sorbitol.
[0017] The compositions of the present invention also include
solvent gels containing 0.2% to 10% of the above di-acetals as a
gelling agent. Solvents useful herein include, as merely examples,
lower monohydric alcohols, polyhydric alcohols, and mixtures
thereof. Water may also be included as a portion of the solvent.
However, the solvent will generally comprise water at levels no
greater than 5% by weight of the final composition. Examples of
solvents which may be utilized in the present invention include
liquid polyethylene glycols (e.g., diethylene glycol, triethylene
glycol), liquid polypropylene glycols (e.g., dipropylene glycol,
tripropylene glycol), liquid polypropylene polyethylene glycol
copolymers, ethanol, n-propanol, n-butanol, t-butanol,
2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,2-butylene
glycol, isopropanol, isobutanol, diethylene glycol, monomethyl
ether, diethylene glycol, monoethylether, 1,3-butylene glycol,
2,3-butylene glycol, 2,4-dihydroxy-2-methylpentane, trimethylene
glycol, glycerine, 1,3-butane diol, 1,4-butane diol, and the like,
and mixtures thereof. As used herein, polyethylene glycols,
polypropylene glycols, and polypropylene polyethylene glycol
copolymers include alkyl ether derivatives of these compounds
(e.g., ethyl, propyl, and butyl ether derivatives). Examples of
such compounds are butyl ether derivatives of polypropylene
polyethylene glycol copolymers, such as PPG-5-buteth-7.
[0018] These solvents are fully described, for example, in U.S.
Pat. No. 4,518,582 to Schamper et al. and European Published
Application 107,330 to Luebbe et al. incorporated herein by
reference. The preferred solvents for use herein include liquid
polyethylene glycols, liquid polypropylene glycols, liquid
polypropylene polyethylene glycol copolymers, propylene glycol,
1,3-butylene glycol, and 2,4-dihydroxy-2-methylpentane (sometimes
referred to as hexylene glycol), and mixtures thereof. Particularly
preferred solvents include propylene glycol, dipropylene glycol,
tripropylene glycol, triethylene glycol, hexylene gylcol, and
mixtures thereof.
[0019] Other organic solvents useful herein include aromatics,
halogenated aromatics, nitrated aromatics, ketones, amines,
nitriles, esters, aldehydes, and mixtures thereof. Examples of
solvents which may be utilized in the present invention include
xylenes (o, m, and p-substituted), 2-chlorotoluene, fluorobenzene,
nitrobenzene, benzonitrile, dimethylsulfoxide (DMSO),
N,N-dimethylformamide (DMF), and 1-methyl-2-pyrrolidinone
(NMP).
[0020] The di-acetals and monoacetals of the present invention may
be prepared by a variety of techniques, some of which are known in
the art. Generally, such procedures employ the reaction of one mole
of D-sorbitol with about 2 moles of aldehyde (for diacetals), with
1 mole of aldehyde for monoacetals, in the presence of an acid
catalyst. The temperature employed in the reaction will vary widely
depending upon the characteristics, such as melting point, of the
aldehyde or aldehydes employed as a starting material in the
reaction. The reaction medium may be an aqueous medium or a
non-aqueous medium. One very advantageous method that can be
employed to prepare di-acetals of the invention is described in
U.S. Pat. No. 3,721,682, to Murai et al. (New Japan Chemical
Company Limited), the disclosure of which is hereby incorporated
herein by reference. While the disclosure of the patent is limited
to benzylidene sorbitols, it has been found that the di-acetals of
the present invention may also be conveniently prepared by the
method described therein. Additional methods for preparing DBS
systems can be found in U.S. Pat. No. 5,731,474 to Scrivens et al.,
U.S. Pat. No. 4,902,807 to Kobayashi et al. which discloses DBS
having an alkyl group or halogen for use as clarifying agents, and
U.S. Pat. No. 5,106,999 to Gardlik et al. which discloses the
preparation of di(meta-fluorobenzylide- ne) sorbitol,
di(meta-chlorobenzylidene) sorbitol, and di(meta-bromobenzylidene)
sorbitol.
[0021] The inventive sorbitol di-acetals and monoacetals prepared
by the above techniques may contain minor impurities (triacetals,
for example). Although it may not always be necessary to remove
these impurities (particularly if they are present in very low
proportions) prior to incorporation of the di-acetal or monoacetal
into the target polyolefin, it may be desirable to do so and such
purification may serve to enhance the transparency of the resin
produced thereby. Purification of the di-acetal may be
accomplished, for instance, by removal of the tri-acetal impurities
by the extraction thereof with a relatively non-polar solvent. By
removal of the impurities, the product may be purified so that the
amount of di-acetal in the additive composition contains at least
about 90 percent and even up to 95 percent di-acetal or more.
[0022] The proportion of di-acetal or monoacetal in the composition
of this invention is an amount sufficient to improve the
transparency of the composition, generally from about 0.01 to about
2 percent by weight, preferably about 0.1 to about 1 percent by
weight, based upon the total weight of the composition may be
provided. When the content of the di-acetal is less than about 0.01
percent by weight, the resulting composition may not be
sufficiently improved in respect to transparency characteristics.
When the content of di-acetal or monoacetal is increased beyond
about 2 percent by weight, no additional advantage can be
observed.
[0023] The polyolefin polymers of the present invention may include
aliphatic polyolefins and copolymers made from at least one
aliphatic olefin and one or more ethylenically unsaturated
comonomers. Generally, the comonomers, if present, constitute a
minor amount, e.g., about 10 percent or less or even about 5
percent or less, of the entire polyolefin, based upon the total
weight of the polyolefin. Such comonomers may serve to assist in
clarity improvement of the polyolefin, or they may function to
improve other properties of the polymer. Examples include acrylic
acid and vinyl acetate, etc. Examples of olefin polymers whose
transparency can be improved conveniently according to the present
invention are polymers and copolymers of aliphatic monoolefins
containing 2 to about 6 carbon atoms which have an average
molecular weight of from about 10,000 to about 2,000,000,
preferably from about 30,000 to about 300,000, such as
polyethylene, linear low density polyethylene, polypropylene,
crystalline ethylenepropylene copolymer, poly(1-butene), 1-hexene,
1-octene, vinyl cyclohexane, and polymethylpentene. The polyolefins
of the present invention may be described as basically linear,
regular polymers that may optionally contain side chains such as
are found, for instance, in conventional, low density
polyethylene.
[0024] Other polymers that may benefit from the nucleation and
clarification properties of the sorbitol acetals of the present
invention include polyethylene terephthalate, polybutylene
terephthalate, and polyamides, among others.
[0025] The olefin polymer or copolymer used in the composition of
the present invention is crystalline, and the diffraction of light
caused by micro crystals contained in it is considered to be
responsible for the deterioration of the transparency of the
polymer. It is thought that the di-acetal functions in the
composition to reduce the size of the microcrystals thereby
improving the transparency of the polymer.
[0026] The composition of the present invention can be obtained by
adding a specific amount of the di-acetal or monoacetal directly to
the olefin polymer or copolymer, and merely mixing them by an
suitable means. Alternatively, a concentrate containing as much as
about 20 percent by weight of the di-acetal in a polyolefin
masterbatch may be prepared and be subsequently mixed with the
resin. Furthermore, the inventive alditol derivatives (and other
additives) may be present in any type of standard polyolefin
additive form, including, without limitation, powder, prill,
agglomerate, liquid suspension, and the like, particularly
comprising dispersion aids such as polyolefin (e.g., polyethylene)
waxes, stearate esters of glycerin, montan waxes, mineral oil, and
the like. Basically, any form may be exhibited by such a
combination or composition including such combination made from
blending, agglomeration, compaction, and/or extrusion.
[0027] Other additives such as a transparent coloring agent or
plasticizers (e.g., dioctyl phthalate, dibutyl phthalate, dioctyl
sebacate, mineral oil, or dioctyl adipate), can be added to the
composition of the present invention so long as they do not
adversely affect the improvement of transparency of the product. It
has been found that plasticizers such as those exemplified above
may in fact aid in the improvement of the transparency by the
di-acetal.
[0028] With regard to other additives it may also be desirable to
employ the di-acetals or monoacetals disclosed above in combination
with other conventional additives having known transparency
improving effects such as, for instance, para-t-butylbenzoic acid,
its salts, low molecular weight waxy polypropylene and the like. It
may even be desirable to provide the particular di-acetals or
monoacetals of the present invention in the polyolefin composition
in combination with the previously described dibenzylidene sorbitol
additive disclosed in U.S. Pat. No. 4,016,118 to Harnada et al. In
such applications, generally at least about 10 percent, preferably
about 25 percent, or even about 50 percent or more of the clarity
improving component will be the diacetals of the present invention,
with the remainder being comprised of other known clarifying
agents, plasticizers, etc.
[0029] The compositions of the present invention may be obtained by
adding the fluorinated and alkylated benzylidene sorbitol acetal to
the polymer or copolymer and merely mixing the resultant
composition by any suitable means. The composition may then be
processed and fabricated by any number of different techniques,
including, without limitation, injection molding, injection blow
molding, injection stretch blow molding, injection rotational
molding, extrusion, extrusion blow molding, sheet extrusion, film
extrusion, cast film extrusion, foam extrusion, thermoforming (such
as into films, blown-films, biaxially oriented films), thin wall
injection molding, and the like into a fabricated article.
[0030] Other additives may also be used in the composition of the
present invention, provided they do not interfere with the primary
benefits of the invention. It may even be advantageous to premix
these additives or similar structures with the nucleating agent in
order to reduce its melting point and thereby enhance dispersion
and distribution during melt processing. Of particular interest is
the incorporation of the inventive symmetrical compound or
compounds with, without limitation to any specific additive
nucleators or clarifiers, selected amounts, for example
bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS),
bis(3,4-dichlorobenzylidene) sorbitol, bis(3,4-difluorobenzylidene)
sorbitol, bis(3-chloro-4-fluorobenzylidene) sorbitol, and
bis(4-chloro-3-fluorobenzylidene) sorbitol. As noted below, such a
combination provides unexpected haze benefits within target
polyolefin (e.g., polypropylene) plastic articles. Such additives
are well known to those skilled in the art, and include
plasticizers, lubricants, catalyst neutralizers, antioxidants,
light stabilizers, colorants, other nucleating agents, and the
like. Some of these additives may provide further beneficial
property enhancements, including improved aesthetics, easier
processing, and improved stability to processing or end use
conditions.
[0031] In particular, it is contemplated that certain organoleptic
improvement additives be added for the purpose of reducing the
migration of degraded benzaldehydes from reaching the surface of
the desired article. The term "organoleptic improvement additive"
is intended to encompass such compounds and formulations as
antioxidants (to prevent degradation of both the polyolefin and
possibly the target alditol derivatives present within such
polyolefin), acid neutralizers (to prevent the ability of
appreciable amounts of residual acids from attacking the alditol
derivatives), and benzaldehyde scavengers (such as hydrazides,
hydrazines, and the like, to prevent the migration of foul tasting
and smelling benzaldehydes to the target polyolefin surface). Such
compounds and formulations can be added in any amounts in order to
provide such organoleptic improvements as needed. However, the
amounts should not appreciably affect the haze results for the
target polyolefin itself. Thus, lower amounts on the order of from
about 20 ppm to about 2,000 ppm of the total polyolefin component
are desired.
[0032] The compositions of the present invention are suitable as
additives to improve the clarity of packaging materials and
container materials for cosmetics, food-stuffs, and the like,
because they give film, sheet, and other fabricated articles having
excellent transparency and physical properties.
PREFERRED EMBODIMENTS OF THE INVENTION
[0033] The following examples further illustrate the present
invention but are not to be construed as limiting the invention as
defined in the claims appended hereto. All parts and percents given
in these examples are by weight unless otherwise indicated.
[0034] DBS Formation
EXAMPLE 1
Preparation of Bis(4-fluoro-3-methylbenzylidene)sorbitol
[0035] A one liter four-necked cylindrical shaped reaction flask
equipped with a Dean-Stark trap, condenser, thermometer, nitrogen
inlet, and a mechanical stirrer was charged with 40.55 g of
sorbitol (0.2226 mole), 600 mL of cyclohexane, 61.50 g of
4-fluoro-3-methylbenzaldehyde (0.4452 moles), 2.90 g of
p-toluenesulfonic acid, 2.4 mL of water, and 210 mL of methanol.
The reaction was stirred and heated under reflux with removal of
water through the Dean Stark trap. The reaction becomes very thick
and additional solvent is added as needed. After about six hours,
the reaction is cooled, neutralized with potassium hydroxide, and
filtered. The wet cake was washed thoroughly with water and
cyclohexane, dried in a vacuum oven at 110.degree. C. to give 74.20
g of Bis(4-fluoro-3-methylben- zylidene)sorbitol (as determined
through Infrared Spectroscopy, Gas Chromatography/Mass
Spectrometry, .sup.1H NMR, and C.sup.13 NMR, all collectively
hereinafter referred to as "standard analyses"). The purity was
about 95% as determined by gas chromatography (GC). The melting
point was determined to be [by Differential Scanning Calorimetry
(DSC) @ 20.degree. C./min] about 237.80.degree. C.
EXAMPLE 2
Preparation of Bis(3-fluoro-4-methylbenzylidene)sorbitol
[0036] A one liter four-necked cylindrical shaped reaction flask
equipped with a Dean-Stark trap, condenser, thermometer, nitrogen
inlet, and a mechanical stirrer was charged with 42.00 g of
sorbitol (0.2306 mole), 600 mL of cyclohexane, 63.70 g of
3-fluoro-4-methylbenzaldehyde (0.4611 moles), 3.00 g of
p-toluenesulfonic acid, 2.5 mL of water, and 210 mL of methanol.
The reaction was stirred and heated under reflux with removal of
water through the Dean Stark trap. The reaction becomes very thick
and additional solvent is added as needed. After about six hours,
the reaction is cooled, neutralized with potassium hydroxide, and
filtered. The wet cake was washed thoroughly with water and
cyclohexane, dried in a vacuum oven at 110.degree. C. to give 85.18
g of Bis(3-fluoro-4- methylbenzylidene)sorbitol (as determined
through standard analyses). The purity was about 95% as determined
by GC. The melting point was determined to be (DSC @ 20.degree.
C./min) about 278.8.degree. C.
EXAMPLE 3
[0037] Preparation of Bis(4-fluoro-3-methylbenzylidene)xylitol
[0038] A one liter four-necked cylindrical shaped reaction flask
equipped with a Dean-Stark trap, condenser, thermometer, nitrogen
inlet, and a mechanical stirrer was charged with 35.08 g of xylitol
(0.2306 mole), 600 mL of cyclohexane, 63.70 g of
4-fluoro-3-methylbenzaldehyde (0.4611 moles), 3.00 g of
p-toluenesulfonic acid, 2.5 mL of water, and 210 mL of methanol.
The reaction was stirred and heated under reflux with removal of
water through the Dean Stark trap. The reaction becomes very thick
and additional solvent is added as needed. After about six hours,
the reaction is cooled, neutralized with potassium hydroxide, and
filtered. The wet cake was washed thoroughly with water and
cyclohexane, dried in a vacuum oven at 110.degree. C. to give 69.46
g of Bis(4-fluoro-3-methylben- zylidene)xylitol (as determined
through standard analyses). The purity was about 95% as determined
by GC. The melting point was determined to be (DSC @ 20.degree.
C./min) about 222.9.degree. C.
EXAMPLE 4
Preparation of 2,4-Mono(4-fluoro-3-methylbenzylidene)sorbitol
[0039] A two liter cylindrical shaped reaction flask equipped with
a mechanical stirrer was charged with 237.37 g of sorbitol (1.303
mole), 250 mL of water, 22.50 g of 4-fluoro-3-methylbenzaldehyde
(0.1629 moles), 40 mL of concentrated HCl, and 0.20 g of
dodecylbenzene sulfonate. The reaction mixture was then stirred for
14 h at 25.degree. C. After neutralization with 56.0 g of KOH,
crude 2,4-Mono(4-fluoro-3-methylbenzyl- idene)sorbitol was filtered
and collected. The crude product was recrystallized from water
several times to give 3.31 g of
2,4-mono(4-fluoro-3-methylbenzylidene)sorbitol having the structure
of: 6
[0040] (through standard analyses). The purity was about 98% as
judged by GC. The melting point was measured (DSC @ 20.degree.
C./min) to be about 178.0.degree. C.
EXAMPLE 5
Preparation of Bis(4-chloro-3-fluorobenzylidene)sorbitol
[0041] A one liter four-necked cylindrical shaped reaction flask
equipped with a Dean-Stark trap, condenser, thermometer, nitrogen
inlet, and a mechanical stirrer was charged with 42.00 g of
sorbitol (0.2306 mole), 600 mL of cyclohexane, 73.11 g of
4-chloro-3-fluorobenzaldehyde (0.4611 moles), 3.00 g of
p-toluenesulfonic acid, 2.5 mL of water, and 210 mL of methanol.
The reaction was stirred and heated under reflux with removal of
water through the Dean Stark trap. The reaction becomes very thick
and additional solvent is added as needed. After about six hours,
the reaction is cooled, neutralized with potassium hydroxide, and
filtered. The wet cake is washed thoroughly with water and
cyclohexane, dried in a vacuum oven at 110.degree. C. to give 93.02
g of Bis(4-chloro-3-fluoroben- zylidene)sorbitol (as determined
through standard analyses). The purity was about 95% as judged by
GC. The melting point was measured (DSC @ 20.degree. C./min) to be
about 262.0.degree. C.
EXAMPLE 6
Preparation of Bis(3-chloro-4-fluorobenzylidene)sorbitol
[0042] A one liter four-necked cylindrical shaped reaction flask
equipped with a Dean-Stark trap, condenser, thermometer, nitrogen
inlet, and a mechanical stirrer was charged with 34.30 g of
sorbitol (0.1883 mole), 600 mL of cyclohexane, 59.70 g of
3-chloro-4-fluorobenzaldehyde (0.3765 moles), 2.50 g of
p-toluenesulfonic acid, 2.1 mL of water, and 210 mL of methanol.
The reaction was stirred and heated under reflux with removal of
water through the Dean Stark trap. The reaction becomes very thick
and additional solvent is added as needed. After about six hours,
the reaction is cooled, neutralized with potassium hydroxide, and
filtered. The wet cake is washed thoroughly with water and
cyclohexane, dried in a vacuum oven at 110.degree. C. to give 39.13
g of Bis(3-chloro-4-fluoroben- zylidene)sorbitol (as determined
through standard analyses). The purity was about 95% as judged by
GC. The compound showed melting transitions (DSC @ 20.degree.
C./min) at 204.8 and 220.0.degree. C.
[0043] Polyolefin Formation and Testing
[0044] Thermoplastic compositions (plaques) and certain gels were
produced comprising a the additives from the EXAMPLEs above and
sample random copolymer polypropylene (RCP) resins, polypropylene
homopolymers (HP), Impact Copolymer (ICP), and Linear Low Density
Polyethylene (LLDPE), produced dry blended in a Welex mixer at
.about.2000 rpm, extruded through a single screw extruder at
400-450.degree. F., and pelletized. Accordingly, one kilogram
batches of target polypropylene were produced in accordance with
the following table:
1 RANDOM COPOLYMER POLYPROPYLENE COMPOSITION TABLE Component Amount
Polypropylene random copolymer flake (3% ethylene) 1000 g (MF = 12)
Irganox .RTM. 1010, Primary Antioxidant (from Ciba) 500 ppm Irgafos
.RTM. 168, Secondary Antioxidant (from Ciba) 1000 ppm Calcium
Stearate, Acid Scavenger 800 ppm Inventive Diacetal (and diacetal
compositions) as noted
[0045] The base resin (random copolymer, hereinafter "RCP") and all
additives were weighed and then blended in a Welex mixer for 1
minute at about 1600 rpm. All samples were then melt compounded on
a Killion single screw extruder at a ramped temperature from about
204.degree. to 232.degree. C. through four heating zones. The melt
temperature upon exit of the extruder die was about 246.degree. C.
The screw had a diameter of 2.54 cm and a length/diameter ratio of
24:1. Upon melting the molten polymer was filtered through a 60
mesh (250 micron) screen. Plaques of the target polypropylene were
then made through extrusion into an Arburg 25 ton injection molder.
The molder molder was set at a temperature anywhere between 190 and
260.degree. C., with a range of 190 to 240.degree. C. preferred,
most preferably from about 200 to 230.degree. C. (for the Tables
below, the standard temperature was 220; a # denotes a temperature
210, a {circumflex over ( )} denotes a temperature of 200, and a @
denotes a temperature of 230). The plaques had dimensions of about
51 mm.times.76 mm.times.1.27 mm, and were made in a mold having a
mirror finish. The mold cooling circulating water was controlled at
a temperature of about 25.degree. C.
[0046] The same basic procedures were followed for the production
of plaques of HP and LLDPE plastics but with the following
compositions:
2 HOMOPOLYMER POLYPROPYLENE COMPOSITION TABLE Component Amount
Polypropylene homopolymer (MFI = 12) (Montell 630) 1000 g Irganox
.RTM. 1010, Primary Antioxidant (from Ciba) 500 ppm Irgafos .RTM.
168, Secondary Antioxidant (from Ciba) 1000 ppm Calcium Stearate,
Acid Scavenger 800 ppm Inventive Diacetal (and diacetal
compositions) as noted
[0047]
3 LINEAR LOW DENSITY POLYETHYLENE COMPOSITION TABLE Component
Amount Dowlex .RTM. 2517 Linear Low Density Polyethylene (with 1000
g Antioxidants and Acid scavengers already supplied) Sodium
Stearate 500 ppm Inventive Diacetal (and diacetal compositions) as
noted
[0048] The haze values were measured by ASTM Standard Test Method
D1003-61 "Standard Test Method for Haze and Luminous Transmittance
of Transparent Plastics" using a BYK Gardner XL-211 Hazemeter.
Nucleation capabilities were measured as polymer recrystallization
temperatures (which indicate the rate of polymer formation provided
by the presence of the nucleating additive) by melting the target
plaques, cooling the plaques at a rate of about 20.degree.
C./minute, and recording the temperature at which polymer
re-formation occurs. Control plaques without alditol additives as
well as 3,4-dimethyldibenzylidene sorbitol (3,4-DMDBS) were
produced for comparative purposes for some or all of the
above-noted measurements. Plaques of various thicknesses (50 mil,
100 mil, and 3 mm) were then prepared by injection molding at
400-430.degree. F. The haze values were measured by ASTM Standard
Test Method D1003-61 "Haze and luminous transmittance of
transparent plastics" using a Gardner Hazemeter. Control plaques
without alditol additives as well as 3,4-dimethyldibenzylidene
sorbitol (3,4-DMDBS), 3,4-dimethyldibenzylidene xylitol
(3,4-DMDBS), dibenzylidene sorbitol (DBS) alone, and NA-11 (a
polyolefin nucleator available from Asahi Denka Co.) containing
plaques, as noted below within the examples, were produced for
comparative purposes for some or all of the above-noted
measurements. An asterisk (*) denotes no measurements were
taken.
4TABLE 1 Part Polym. Ex. Additive - from Conc. Haze Resin Thick.
Recryst. No. Example # above (%) (%) Grade (mil) Temp. 4 Control --
60.9 RCP 50 94.6 5 2 .15 16.9 RCP 50 * 6 2 .25 7.8 RCP 50 111.8 7 2
.35 7.2 RCP 50 112.2 8 2 .50 7.0 RCP 50 *
[0049]
5TABLE 2 Part Polym. Ex. Additive - from Conc. Haze Resin Thick.
Recryst. No. Example # above (%) (%) Grade (mil) Temp. 9 Control
(#) -- 59.8 RCP 50 94.3 10 1 (#) .16 19.2 RCP 50 * 11 1 (#) .24 8.6
RCP 50 * 12 1 (#) .30 7.1 RCP 50 114.1 13 1 (#) .40 6.8 RCP 50
114.3
[0050]
6TABLE 3 Part Polym. Ex. Additive - from Conc. Haze Resin Thick.
Recryst. No. Example # above (%) (%) Grade (mil) Temp. 14 Control
({circumflex over ( )}) -- 61.3 RCP 50 95.1 15 3 ({circumflex over
( )}) .15 55.6 RCP 50 * 16 3 ({circumflex over ( )}) .25 49.1 RCP
50 * 17 3 ({circumflex over ( )}) .35 45.7 RCP 50 * 18 3
({circumflex over ( )}) .50 38.0 RCP 50 108.1 19 3,4-DMDBX
({circumflex over ( )}) .50 25.0 RCP 50 109.4
[0051]
7TABLE 4 Part Ex. Additive - from Example Conc. Haze Resin Thick.
No. # above (%) (%) Grade (mil) 20 Control -- 90.7 RCP 100 21 1 .25
30.0 RCP 100 22 1 .35 28.4 RCP 100 23 1 .45 27.2 RCP 100 24 5 (#)
.12 26.1 RCP 50 25 5 (#) .16 12.4 RCP 50 26 5 (#) .24 8.0 RCP 50 27
5 (#) .30 7.6 RCP 50 28 5 (#) .40 7.3 RCP 50 29 6 .25 17.0 RCP 50
30 6 .35 10.4 RCP 50 31 6 .50 8.3 RCP 50
[0052]
8TABLE 5 Part Polym. Ex. Additive - from Conc. Haze Resin Thick.
Recryst. No. Example # above (%) (%) Grade (mil) Temp. 32 None (@)
-- 78.1 HP 50 107.9 33 1 (@) .25 19.4 HP 50 121.9 34 1 (@) .35 11.5
HP 50 125.3 35 1 (@) .50 10.0 HP 50 * 36 4 (@) .25 67.7 HP 50
110.3
[0053]
9TABLE 6 Part Polym. Flex. Ex. Additive - from Conc. Resin Thick.
Recryst. Mod. No. Example # above (%) Grade (mm) Temp. (MPa) 37
None (@) -- ICP 3.0 107.9 1005 38 1 (@) .20 ICP 3.0 115.2 1138 39 1
(@) .25 ICP 3.0 121.3 1179 40 1 (@) .35 ICP 3.0 124.5 1207 41 NA-11
.10 ICP 3.0 122.8 1158
[0054]
10TABLE 7 Part Polym. Ex. Additive - from Conc. Haze Resin Thick.
Recryst. No. Example # above (%) (%) Grade (mil) Temp. 42 None
({circumflex over ( )}) -- 93.9 LLDPE 50 99.0 43 1 ({circumflex
over ( )}) .15 55.3 LLDPE 50 * 44 1 ({circumflex over ( )}) .20
47.1 LLDPE 50 * 45 1 ({circumflex over ( )}) .25 47.6 LLDPE 50
108.1 46 1 ({circumflex over ( )}) .15 51.9 LLDPE 50 * 47 1
({circumflex over ( )}) .20 53.6 LLDPE 50 * 48 3,4-DMDBS
({circumflex over ( )}) .25 53.6 LLDPE 50 108.3 49 DBS ({circumflex
over ( )}) .15 63.0 LLDPE 50 * 50 DBS ({circumflex over ( )}) .25
62.6 LLDPE 50 106.1
[0055] Thus, the inventive fluoro-alkyl alditol derivatives
provided similar, if not better, characteristics within the target
thermoplastics as compared with the control and other compositions
comprising other types of clarifying and/or nucleating
additives.
[0056] Gel Formation Examples
[0057] Solid gels were also produced comprising the inventive
alditol derivatives through recognized, simple methods. In
particular, specific organic solvents were combined with the
additives in certain concentrations and mixed thoroughly. The
resultant mixture was then heated to a temperature between about
170.degree. F. (77.degree. C.) and 300.degree. F. (149.degree. C.),
as indicated below, under agitation for between 5 and 120 minutes.
The resultant solution was then poured into a mold to produce a gel
stick. The solvents listed below are not intended to be exhaustive
as to the potential types which may be utilized to form gels with
the inventive alditol derivatives, and thus are merely listed as
preferred solvents for such purposes. The examples below were
analyzed empirically and by touch to determine if a gel actually
formed and the hardness properties as well as any formed gels.
11TABLE 8 Additive - DBS Gel from Conc. For- Gel Ex. Example
(weight mation Character No. Solvent # above %) (Y/N) (Hard/Soft)
51 1,2-Propanediol 1 0.5 Y S 52 1,2-Propanediol 1 1 Y H 53
1,2-Propanediol 1 2 Y H 54 1,2-Propanediol 1 3 Y H 55
1,2-Propanediol 1 5 Y H 56 1,3-Propanediol 1 0.5 N -- 57
1,3-Propanediol 1 1 Y S 58 1,3-Propanediol 1 2 Y H 59
1,3-Propanediol 1 3 Y H 60 1,3-Propanediol 1 5 Y H 61 Triethylene
Glycol 1 0.5 N -- 62 Triethylene Glycol 1 1 N -- 63 Triethylene
Glycol 1 2 Y H 64 Triethylene Glycol 1 3 Y H 65 Triethylene Glycol
1 5 Y H 66 Poly(ethyleneglycol) 1 0.5 N -- 67 Poly(ethyleneglycol)
1 1 N -- 68 Poly(ethyleneglycol) 1 2 Y H 69 Poly(ethyleneglycol) 1
3 Y H 70 Poly(ethyleneglycol) 1 5 Y H 71 1-Butanol 1 0.5 Y S 72
1-Butanol 1 1 Y S 73 1-Butanol 1 2 Y H 74 1-Butanol 1 3 Y H 75
1-Butanol 1 5 Y H 76 Mineral Oil 1 0.5 Y S 77 Mineral Oil 1 1 Y S
78 Mineral Oil 1 2 Y S 79 Mineral Oil 1 3 Y S 80 Mineral Oil 1 5 Y
S 81 Xylene 1 0.5 Y S 82 Xylene 1 1 Y S 83 Xylene 1 2 Y S 84 Xylene
1 3 Y S 85 Xylene 1 5 Y S 86 2-Chlorotoluene 1 0.5 Y S 87
2-Chlorotoluene 1 1 Y S 88 2-Chlorotoluene 1 2 Y H 89
2-Chlorotoluene 1 3 Y H 90 2-Chlorotoluene 1 5 Y H
[0058]
12TABLE 9 Additive - DBS Gel from Conc. For- Gel Ex. Example
(weight mation Character No. Solvent # above %) (Y/N) (Hard/Soft)
91 1,2-Propanediol 2 0.5 Y S 92 1,2-Propanediol 2 1 Y H 93
1,2-Propanediol 2 3 Y H 94 1,3-Propanediol 2 0.5 N -- 95
1,3-Propanediol 2 1 Y H 96 1,3-Propanediol 2 3 Y H 97 1-Butanol 2
0.5 Y S 98 1-Butanol 2 1 Y H 99 1-Butanol 2 3 Y H 100
2-Chlorotoluene 2 0.5 Y S 101 2-Chlorotoluene 2 1 Y S 102
2-Chlorotoluene 2 3 Y S 103 Nitrobenzene 2 0.5 Y H 104 Nitrobenzene
2 1 Y H 105 Nitrobenzene 2 3 Y H 106 Benzonitrile 2 0.5 Y S 107
Benzonitrile 2 1 Y H 108 Benzonitrile 2 3 Y H
[0059] Thus, the inventive fluoro-alkyl alditol derivatives provide
excellent gelling capabilities for solvents, depending on their
concentration without the target solvents.
[0060] Compositions with Other Clarifiers
[0061] Formulations of the inventive compound from Example 1 above
were then produced incorporating other polyolefin clarifying
benzylidene derivative compounds (such as DMDBS, etc., as listed in
the Table below) in various proportions. RCP polypropylene was
compounded as noted above (with lower molder barrel temperatures of
about 200.degree. C. marked with a #) but with mixtures of such
other clarifiers and the inventive compounds of Example 1 into 50
mil and 100 mil plaques. Haze measurements were taken as noted
above as well. The other clarifier compounds added within the
samples below are as follows:
[0062] A--DMDBS
[0063] B--Bis(3,4-dichlorobenzylidene) sorbitol
[0064] C--Bis(3,4-difluorobenzylidene) sorbitol
[0065] D--Bis(3-chloro-4-fluorobenzylidene) sorbitol
[0066] E--Bis(4-chloro-3-fluorobenzylidene) sorbitol
[0067] The haze results for such mixed formulations within target
RCP plaques are tabulated below:
13TABLE 10 Physical Mixtures Inventive DBS Compounds And Other
Polyolefin Clarifiers Additive (Example # from above) mixed with
other Polym. Test clarifiers (letter from Part Recryst. Plaque
above) (plus ratio of Conc. Haze Resin Thick Temp. No. Additive to
clarifier) (%) (%) Grade (mil) (.degree. C.) 109 1 plus A [50/50]
.2 7.3 RCP 50 * 110 1 plus A [50/50] .25 6.6 RCP 50 * 111 1 plus A
[50/50] .35 6.3 RCP 50 112.1 112 1 plus A [50/50] .5 6.6 RCP 50 *
113 1 plus A [50/50] .15 33.5 RCP 100 * 114 1 plus A [50/50] .2
22.4 RCP 100 * 115 1 plus A [50/50] .25 18.8 RCP 100 112.1 116 1
plus A [50/50] .35 22.3 RCP 100 * 117 1 plus B [50/50] # .35 6.4
RCP 50 * 118 1 plus B [50/50] # .5 6.6 RCP 50 * 119 1 plus C
[50/50] # .35 8.1 RCP 50 * 120 1 plus C [50/50] # .5 7.7 RCP 50 *
121 1 plus D [50/50] # .35 8.0 RCP 50 * 122 1 plus D [50/50] # .5
6.9 RCP 50 * 123 1 plus E [50/50] # .35 7.7 RCP 50 * 124 1 plus E
[50/50] # .5 7.0 RCP 50 *
[0068] Thus, the inventive compound also exhibited excellent haze
measurements in polypropylene in the presence of another clarifying
agent.
[0069] There are, of course, many alternative embodiments and
modifications of the present invention which are to be included
within the spirit and scope of the following claims.
* * * * *