U.S. patent application number 14/336237 was filed with the patent office on 2014-11-13 for preparation of metallic comonomers for polystyrene.
The applicant listed for this patent is FINA TECHNOLOGIES, INC.. Invention is credited to Jason Clark, Scott Cooper, Steven D. Gray.
Application Number | 20140336344 14/336237 |
Document ID | / |
Family ID | 48467432 |
Filed Date | 2014-11-13 |
United States Patent
Application |
20140336344 |
Kind Code |
A1 |
Gray; Steven D. ; et
al. |
November 13, 2014 |
PREPARATION OF METALLIC COMONOMERS FOR POLYSTYRENE
Abstract
A method for making a polystyrene ionomer comprises: preparing a
metallic comonomer within styrene monomer to form a reaction
mixture; and placing the reaction mixture under conditions suitable
for the formation of a polymer composition. The metallic comonomer
can be a metal acrylate, formed by contacting a metal complex and
an acrylate precursor.
Inventors: |
Gray; Steven D.; (Florence,
KY) ; Cooper; Scott; (Humble, TX) ; Clark;
Jason; (Houston, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FINA TECHNOLOGIES, INC. |
Houston |
TX |
US |
|
|
Family ID: |
48467432 |
Appl. No.: |
14/336237 |
Filed: |
July 21, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13306088 |
Nov 29, 2011 |
8829114 |
|
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14336237 |
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Current U.S.
Class: |
526/240 |
Current CPC
Class: |
C08F 230/04 20130101;
C08F 212/08 20130101; C08F 212/08 20130101; C08F 212/08 20130101;
C08F 230/00 20130101; C08F 220/06 20130101 |
Class at
Publication: |
526/240 |
International
Class: |
C08F 230/04 20060101
C08F230/04 |
Claims
1-26. (canceled)
27. A method comprising: providing a first feed comprising styrene
monomer and a metal complex; providing a second feed comprising
styrene monomer and an acrylate precursor; mixing the first feed
and the second feed to form a reaction mixture; introducing the
reaction mixture to a contacting vessel for a residence time
sufficient for in situ formation of a metal acryalate; and
introducing the reaction mixture to a polymerization reactor.
28. (canceled)
29. The method of claim 27, wherein the residence time ranges from
15 minutes to 1 hour.
30. The method of claim 27, further comprising polymerizing the
reaction mixture in the polymerization reactor to form a
polystyrene ionomer.
31. The method of claim 30, wherein the polymerizing of the
reaction mixture is carried out in a solution or mass
polymerization process.
32. The method of claim 30, wherein the polymerizing of the
reaction mixture is carried out at a temperature ranging from
70.degree. C. to 240.degree. C.
33. The method of claim 27, wherein the metal complex is a compound
having a general chemical formula M(NR.sub.5R.sub.6).sub.n, wherein
n is a metal formal oxidation state and R.sub.5 and R.sub.6 are
each independently alkyl groups, aryl groups, substituted alkyl
groups, substituted aryl groups, derivatives thereof or
combinations thereof.
34. The method of claim 27, wherein the metal complex is an
organometallic compound represented by the formula MA.sub.nL.sub.y,
wherein M is a main group or transition element of groups 3 to 12
of the periodic table, wherein A is a monoanioic ligand, wherein n
is a metal formal oxidation state from +2 to +6, and wherein L is
an optional additional ligand.
35. The method of claim 27, wherein the acrylate precursor
comprises an acrylic acid, and wherein the metal complex is an
organometallic compound that irreversibly reacts with the acrylic
acid selected from dibutylmagnesium (MgBu.sub.2), triethyl aluminum
(AlEt.sub.3), tetrabenzyl zirconium, TaMg.sub.5, WMe.sub.6, and
[Zn(CH.sub.2Ph.sub.4)].
36. The method of claim 27, wherein the acrylate precursor
comprises an acrylic acid, and wherein the metal complex is a
material that liberates conjugate acids weaker than the acrylic
acid.
37. The method of claim 27, wherein the metal complex is a compound
having a general chemical formula M(OR.sub.4).sub.n, wherein n is a
metal formal oxidation state and R.sub.4 an alkyl group, aryl
group, substituted alkyl group, substituted aryl group, derivative
thereof or combinations thereof.
38. The method of claim 27, wherein the metal complex is a
non-homoleptic alkoxide and amide complex having the structure
Zr(OPh).sub.n,(OBu).sub.4-6.
39. The method of claim 27, wherein the metal complex is a material
that upon reaction with the acrylate precursor produce species with
a decreased acidity with respect to the starting compounds.
40. The method of claim 39, wherein the material comprises a metal
alkoxide comprising an aryl group, a metal amide comprising an aryl
group, or a compound comprising a siloxide.
41. The method of claim 27, wherein the metal complex is
Mg(OEt).sub.2, Al(OiPr).sub.3, Ti(OBu).sub.4, Ta(NMe.sub.2).sub.5,
W(OiBu).sub.6 or Ti(NEt.sub.2).sub.4.
42. The method of claim 27, wherein the metal complex comprises
Ti(OBu).sub.n(NEt.sub.2).sub.4-n, or
Zr(CH.sub.2Ph).sub.2(OPh).sub.2.
43. The method of claim 27, wherein the metal complex comprises
MgAl.sub.2(OR).sub.x or MgZr(OR).sub.x.
44. The method of claim 27, wherein the metal complex is selected
from the group consisting of dibutylmagnesium (MgBu.sub.2),
triethyl aluminum (AlEt.sub.3), tetrabenzyl zirconium
(Zr(CH.sub.2Ph.sub.4)), Mg(OEt).sub.2, Ti(OBu).sub.4,
Ti(NEt.sub.2).sub.4, Zr(OPh).sub.n(OBu).sub.4-n wherein n is at
least 1, Ti(OBu).sub.n(NEt.sub.2).sub.4-n wherein n is at least 1,
Zn(CH.sub.2Ph).sub.2(OPh).sub.2, Mg(Et).sub.2, Mg(BuEt), Mg(n-Hex),
Al(Me).sub.3, Al(iPr).sub.3, or combinations thereof.
45. The method of claim 27, wherein the metal complex is selected
from the group consisting of dibutylmagnesium (MgBu.sub.2),
triethyl aluminum (AlEt.sub.3), tetrabenzyl zirconium
(Zr(CH.sub.2Ph.sub.4)), Mg(OEt).sub.2, Ti(OBu).sub.4,
Ti(NEt.sub.2).sub.4, Zn(CH.sub.2Ph).sub.2(OPh).sub.2, Mg(Et).sub.2,
Mg(BuEt), Mg(n-Hex), Al(Me).sub.3, Al(iPr).sub.3, or combinations
thereof.
46. The method of claim 27, wherein the acrylate precursor
comprises an acrylic acid.
47. The method of claim 27, wherein the metal acrylate is
Zr[O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(OiPr).sub.2.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is related to U.S. Pat. No.
7,601,788 filed Oct. 31, 2007, which is continuation of U.S. Pat.
No. 7,309,740 filed Dec. 13, 2006 which was a divisional of U.S.
Pat. No. 7,179,873 filed Jan. 26, 2005 each of which is entitled
"Branched Ionomers" and each of which is incorporated herein by
reference.
FIELD
[0002] The present invention generally relates to the preparation
of polystyrene copolymers, specifically ionomers, containing
metallic comonomers.
BACKGROUND
[0003] General purpose polystyrene (GPPS) is a polymer made from
styrene, a vinyl aromatic monomer that can be produced from
aromatic hydrocarbons, for example those derived from petroleum.
GPPS is useful in a variety of applications, such as casing for
appliances, molded into toys or utensils, or expanded to create
foamed styrene. In most cases, GPPS is a hard and brittle plastic,
however, the use of comonomers may alter its physical properties.
Ionic comonomers, for example, may alter the properties of a
polymer, such as melt flow rate, melt strength, polydispersity, and
glass transition temperature.
[0004] Metal acrylates are an example of ionic comonomers that can
be used to create a polystyrene branched ionomer. Zinc
dimethacrylate (ZnDMA), for instance, is well known in the art as
useful ionic comonomer for polystyrene production. Several
drawbacks are associated with the use of prepared ZnDMA. ZnDMA can
be expensive. Particles of ZnDMA powder tend to be less than 10
microns in diameter, causing inhalation hazards during transport to
the reaction vessel due to dust. Further, ZnDMA does not easily
dissolve into styrene. Feeding slurries of pre-formed ZnDMA
comonomer to the reactor can be difficult; the ZnDMA may not
suspend well and the consistency in feed concentration may be
questionable. Swings in melt index can occur. In the reaction
vessel, sticking of the methacrylate particles to the vessel
surfaces can occur during mixing due to the static charge build-up
on the surface of these polar compounds, resulting in gel formation
and reactor fouling. Other metal acrylates can also have problems
similar to those of ZnDMA when used as ionic comonomers for
polystyrene.
[0005] Varying parameters such as reaction conditions, type and/or
quantities of comonomer used may allow for the production of
styrenic copolymer compositions tailored to meet the needs of a
wide-range of end-use applications. Thus, an ongoing need exists
for compositions and methodologies for the production of styrenic
copolymers having improved properties.
SUMMARY
[0006] Disclosed herein is a method for the in situ preparation of
a metallic comonomer comprising: contacting chemical precursors of
a metallic comonomer in at least one reaction vessel containing
styrene monomer; and producing a product comprising the metallic
comonomer in solution with the styrene monomer. The in situ
generated metallic comonomer can be a metal acrylate. The in situ
generated metallic comonomer can be prepared via the contacting of
a metal complex and an acrylate precursor, such as acrylic
acid.
[0007] The metal complex may be selected from the group consisting
of an organometallic compound comprising alkyl groups, aryl groups,
alkoxides, amides or combinations thereof; organometallic compounds
that react irreversibly with acrylic acids; materials that liberate
conjugate acids weaker than its starting acrylic acid; compounds
having a general chemical formula MR.sub.n, M(OR.sub.4).sub.n and
M(NR.sub.5R.sub.6).sub.n wherein n is metal formal oxidation state
and R, R.sub.4, R.sub.5 and R.sub.6 are each independently alkyl
groups, aryl groups, substituted alkyl groups, substituted aryl
groups, derivatives thereof or combinations thereof; non-homoleptic
alkoxide and amide complexes; and combinations thereof. The metal
in the metal complex may be selected from the group consisting of
main group metals, metals from groups 3 to 12 of the periodic
table, and combinations thereof. the metal complex is selected from
the group consisting of dibutylmagnesium (MgBu.sub.2), triethyl
aluminum (AlEt.sub.3), tetrabenzyl zirconium
[Zn(CH.sub.2Ph.sub.4)], Mg(OEt).sub.2, Al(O.sup.iPr).sub.3,
Ti(OBu).sub.4, Ti(NEt.sub.2).sub.4, Zr(OPh).sub.n(OBu).sub.4-n,
Ti(OBu).sub.n(NEt.sub.2)4-n, Zn(CH.sub.2Ph).sub.2(OPh).sub.2,
Mg(Et).sub.2, Mg(BuEt), Mg(n-Hex), Al(Me).sub.3, Al(iPr).sub.3, or
combinations thereof.
[0008] The acrylate precursor compound can be an acrylic acid. The
acrylic acid can have the general formula
##STR00001##
[0009] where R.sub.1, R.sub.2, and R.sub.3 may be the same or
different and may each independently be hydrogen, an alkyl group,
an aryl group, a substituted alkyl group, a substituted aryl group,
derivatives thereof, or combinations thereof.
[0010] The acrylate precursor compound may be selected from the
group consisting of methylacrylic acid, octyl acrylic acid, nonyl
acrylic acid, decyl acrylic acid, undecyl acrylic acid, dodecyl
acrylic acid, isodecyl methylacrylic acid, undecyl methylacrylic
acid, stearyl methylacrylic acid and combinations thereof.
[0011] The metal complex and acrylate precursor can react according
to the following equation
##STR00002##
[0012] where: M is a main group or transition metal, n is a formal
oxidation state of a metal, A is a monoanionic ligand that is an
alkoxy, aryloxy, amide, arylamide, or their derivatives, R.sub.1,
R.sub.2, and R.sub.3 are hydrogen, alkyl, or aryl groups, and L is
an additional ligand.
[0013] When x=n, no monoanionic ligand A is present in the metallic
comonomer. When x<n, monoanionic ligand A is present in the
metallic comonomer. In an embodiment, the metallic comonomer is of
the latter type. Examples include
[0014] Zr[O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(OBu).sub.2,
Zr[O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(OiPr).sub.2,
Al[(O.sub.2C(CH.sub.3)+CH.sub.2].sub.2(OiPr).
[0015] The metallic comonomer can have the general formula:
M.sup.n(O.sub.2C--CR.sub.1.dbd.CR.sub.2R.sub.3).sub.xA.sub.n-xL.sub.y
[0016] where: M is a main group or transition metal; n is a formal
oxidation state of a metal (+2 to +6); x is 1-5; A is a monoanionic
ligand, such as an alkoxy, aryloxy, amide, arylamide, or their
derivatives; R.sub.1, R.sub.2, and R.sub.3 are hydrogen, alkyl, or
aryl groups; and L is an optional additional ligand (y can be 0,
when no additional ligand is desired).
[0017] In an embodiment, additional ligand L is a Lewis base donor
selected from the group consisting of THF, alcohols, amines,
phosphines, and similar lewis bases.
[0018] In an embodiment, the acrylate precursor is methacrylic acid
and the metal complex is aluminum isopropoxide, and the resultant
metallic comonomer is aluminum methacrylate.
[0019] The metallic comonomer may be present in an amount of from
100 ppm to 2000 ppm. The styrene may be present in an amount of
from 1 wt. % to 99 wt. % based on the total weight of the polymer
composition. The method may further include contacting the reaction
mixture with an elastomer. The elastomer may be derived from the
group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2
chloro-1,3 butadiene, 2-methyl-1,3-butadiene, 2
chloro-1,3-butadiene, aliphatic conjugated diene monomers, and
combinations thereof.
[0020] The product may be polymerized to form a polystyrene
ionomer, which in turn may be used to produce an article.
[0021] The metal complex and acrylate precursor may be contacted in
close temporal and/or physical proximity of reaction zone, or
alternatively within a reaction zone. In another arrangement, each
of a metal complex and an acrylate precursor are mixed with styrene
monomer to form two styrene solutions, which are contacted within a
reaction zone.
BRIEF DESCRIPTION OF DRAWINGS
[0022] FIG. 1 is a schematic view of one embodiment of a reactor
system.
[0023] FIG. 2 is a schematic of the feed system of Example 1.
[0024] FIGS. 3 and 4 are graphs of hauloff force as a function of
hauloff speed for samples from the example.
[0025] FIG. 5 is graph showing Mz and polydispersity as a function
of aluminum concentration for samples from the example.
DETAILED DESCRIPTION
[0026] The present invention in its many embodiments is directed
towards the production of a polystyrene ionomer. Generally, the
polystyrene ionomer is made via formation of a metallic comonomer
within a monomer such as a styrene monomer and subsequent
contacting of the metallic comonomer with styrene monomer and
optionally other components in a reaction zone under conditions
suitable for the formation of a polymeric composition.
[0027] When ionic comonomers are used, the polymer product can be
referred to as an ionomer. An ionomer is a polymer that contains
nonionic repeating units and a small portion of ionic repeating
units. Generally, the ionic groups make up less than 15% of the
polymer. The ionic groups are attached to the polymer backbone at
random intervals and can create secondary chain interactions, in
which the polar groups reversibly associate with one another,
creating reversible crosslinks. Because of these crosslinks, or
branches, ionomers can also be referred to as branched
ionomers.
[0028] The reversible crosslinks likely are broken with heat and
shear during extrusion but reform upon cooling. Branched ionomers
can thus be melt processed like low molecular weight polystyrene
but have the relatively higher melt strength and other improved
properties expected for branched or higher molecular weight
polystyrene materials. In addition, branches or crosslinks in
styrene-based polymers may exhibit enhance properties such as shear
thinning, bending modulus, tensile strength, impact resistance,
glass transition temperature, and melt viscosity.
[0029] A group of ionic comonomers that can be used in polystyrene
branched ionomers is carboxylate salts with at least one
unsaturated moiety. The unsaturated moiety allows the comonomer to
be incorporated into a growing polystyrene chain during radical
polymerization, while the carboxylate salt is an ionic moiety
capable of providing reversible crosslinks between polystyrene
chains.
[0030] Polystyrene ionomers can be made using many metallic
comonomers. These metallic comonomers generally are made up of an
unsaturated moiety, an anionic moiety, and a cationic moiety. In an
embodiment, the metallic comonomer is a carboxylate salt. The
cationic moiety can be a metal ion associated with the anionic
moiety of a carboxylic acid. The unsaturated moiety is a
carbon-carbon double bond occurring in a chain of at least two
carbon atoms connected to the carboxylic acid. The comonomer can be
a metal acrylate.
[0031] In one embodiment, the metallic comonomer is a metal
acrylate that has the general formula
M.sup.n(O.sub.2C--CR.sub.1.dbd.CR.sub.2R.sub.3).sub.xA.sub.n-xL.sub.y
[0032] where: M is a main group or transition metal; n is a formal
oxidation state of a metal (+2 to +6); x is 1-5; A is a monoanionic
ligand, such as an alkoxy, aryloxy, amide, arylamide, or their
derivatives; R.sub.1, R.sub.2, and R.sub.3 are hydrogen, alkyl, or
aryl groups; and L is an optional additional ligand (y=0-6; y can
be 0, when no additional ligand is desired).
[0033] Examples of acrylate containing compounds suitable for use
in this disclosure include without limitation, compounds having
M=Zn; n=2; x=2; R.sub.1=methyl; and R.sub.2 and R.sub.3=H (for
instance, ZnDMA); compounds having M=Zr; n=4; x=4; R.sub.1=methyl;
and R.sub.2 and R.sub.3=H (for instance, Zr((MA).sub.4); compounds
having M=Zr; n=4; x=2; R.sub.1=methyl; R.sub.2, R.sub.3=H;
A=butoxide (for instance, Zr(MA).sub.2(OBu).sub.2); compounds
having M=Zr; n=4; x=2; R.sub.1=methyl; R.sub.2, R.sub.3=H;
A=isopropyl alkoxide (for instance, Zr(MA).sub.2(OiPr).sub.2); or
combinations thereof. Nonlimiting examples of acrylate containing
compounds suitable for use in this disclosure include zinc
diacrylate, zinc dimethacrylate, and the like.
[0034] The final characteristics of the polystyrene ionomer depend
in part on the nature and amount of metallic comonomer used and may
be tailored by one of ordinary skill in the art with the benefits
of the present disclosure to meet a user and/or process desired
need. For example when the metallic comonomer contains a metal
acrylate, such tailoring may involve modifications to the amount of
metal acrylate used in the polystyrene ionomer, the valence or
formal oxidation state (.sup.n) of metal (M) employed, the steric
and electronic features of acrylate substituents (R.sup.1, R.sup.2,
R.sup.3), the steric and electronic nature of additional metal
ligands (A, L), or combinations thereof.
[0035] In an embodiment the metallic comonomer is present in an
amount of from 100 ppm to 2000 ppm, alternatively from 200 ppm to
1500 ppm, alternatively from 300 ppm to 800 ppm based on total
polymer composition.
[0036] The metallic comonomer may be prepared using any method
compatible with the other components in the polystyrene ionomer. In
an embodiment, the metallic comonomer is prepared by the contacting
of a metal complex and a metal carboxylate precursor. The metallic
comonomer may be prepared in situ, which can mean in temporal
and/or physical proximity to the reaction zone into which it will
be used. The methodologies disclosed herein for the preparation of
the metallic comonomer may provide numerous advantages such as
reducing the handling of toxic materials and preventing the need
for storage of these materials.
[0037] The metal acrylate may be prepared by contacting a metal
complex and an acrylate precursor. In an embodiment, the acrylate
precursor includes acrylic acid. Examples of acrylic acids suitable
for this process include those of the general formula shown in
Structure 1 where R.sup.1, R.sup.2, and R.sup.3 may be the same or
different and may each independently be hydrogen, an alkyl group,
an aryl group, a substituted alkyl group, a substituted aryl group,
derivatives thereof, or combinations thereof. For example, the
acrylate precursor may be methylacrylic acid where R.sup.1 is a
methyl group (CH.sub.3), and R.sup.2 and R.sup.3 are hydrogen
atoms. Examples of other suitable acrylate precursors include octyl
acrylic acid, nonyl acrylic acid, decyl acrylic acid, undecyl
acrylic acid, dodecyl acrylic acid, isodecyl methacrylic acid,
undecyl methacrylic acid, stearyl methacrylic acid, or combinations
thereof.
##STR00003##
[0038] Many metal-containing complexes can be used for the in-situ
generation of a metallic comonomer, which may improve the
flexibility and the range of options when forming comonomers. Many
metal complexes are relatively inexpensive and can dissolve in
styrene. Thus, in-situ generated metallic comonomers of the present
invention can incur a lower cost and have greater solubility, in
comparison to conventional metallic comonomers, such as ZnDMA.
[0039] In an embodiment, the metal complex includes an
organometallic compound. The metal complex can be represented as
MA.sub.nL.sub.y, wherein M is a main group or transition element
such as those found in groups 3 to 12 of the periodic table; A is a
monoanioic ligand; n is a metal formal oxidation state from +2 to
+6, and L is an optional additional ligand. Organometallic
compounds suitable for use in this disclosure include without
limitation metal compounds including alkyl groups, aryl groups,
alkoxides, amides or combinations thereof. The metal complex may
include organometallic compounds that irreversibly react with
acrylic acids. Examples of such compounds include dibutylmagnesium
(MgBu.sub.2), triethyl aluminum (AlEt.sub.3), tetrabenzyl
zirconium, TaMg.sub.5, WMe.sub.6, and [Zn(CH.sub.2Ph.sub.4)].
[0040] In an embodiment, the organometallic compounds can be
materials that liberate conjugate acids weaker than acrylic acid
and also small molecules that are easily distilled. Liberating
conjugate acids weaker than the starting acrylic acids may favor
rapid metathesis. Examples of such compounds include alkoxide and
amide species, in which the monoanionic ligand (A) has the general
chemical formula (OR.sub.4) or (NR.sup.5R.sup.6) respectively
wherein O is oxygen; N is nitrogen; and R.sup.4, R.sup.5 and
R.sup.6 are each independently alkyl groups, aryl groups,
substituted alkyl groups, substituted aryl groups, derivatives
thereof or combinations thereof. Examples of such compounds include
Mg(OEt).sub.2, Al(OiPr).sub.3, Ti(OBu).sub.4, Ta(NMe.sub.2).sub.5,
W(OiBu).sub.6 and Ti(NEt.sub.2).sub.4.
[0041] In another embodiment, the organometallic compounds include
non-homoleptic alkoxide and amide complexes such as for example
Zr(OPh).sub.n,(OBu).sub.4-n. In yet another embodiment, the
organometallic compound includes metal complexes that upon reaction
with the acrylate precursor produce species with a decreased
acidity with respect to the starting compounds. Examples of such
compounds include metal alkoxides or metal amides comprising aryl
groups and compounds comprising siloxides. In yet another
embodiment, the organometallic compound includes a mixture of
complexes having the properties described previously. Examples of
such complexes include Ti(OBu).sub.n(NEt.sub.2).sub.4-n,
Zr(CH.sub.2Ph).sub.2(OPh).sub.2. Other examples include
MgAl.sub.2(OR).sub.x and MgZr(OR).sub.x which are double metal
alkoxides commercially available from Gelest Chemicals.
[0042] Additional ligands, L, in the metal complex may be employed
to fine tune solubility and reactively as well as final product
properties. Examples of L-ligands may include Lewis base donors
such as THF, alcohols, amines, and the like.
[0043] Various factors may be considered by one of ordinary skill
in the art in the selection of the metal to employ in the formation
of the metal acrylate. For example, in determining suitable
transition metal precursors, the relative ease at which the metal's
ligands are displaced to form carboxylate species upon reaction
with the acrylate precursor may be considered.
[0044] The reaction between the metal complex and the acrylate
precursor may be generally represented by Equation 1:
##STR00004##
[0045] where: M is a main group or transition metal; n is a formal
oxidation state of a metal (+2 to +6); x is 1-5; A is a monoanionic
ligand; R.sub.1, R.sub.2, and R.sub.3 are hydrogen, alkyl, or aryl
groups; and L is an optional additional ligand. For example, a
metal complex such as Zr(O.sup.iPr).sub.4 (M=Zr, R=.sup.iPr, n=4)
can be treated with the appropriate level of methyl acrylic acid
(R.sup.1=CH.sub.3 and R.sup.2, R.sup.3=H) to afford the mono (m=1),
di (m=2), tri (m=3), or tetrakis (m=4) substituted zirconium
acrylate with the substitution being based on the final polymer
property requirements. In an embodiment, azeotropic removal of the
isopropanol byproduct is used to control the reaction. In an
alternative embodiment, an excess of methyl acrylic acid is used to
drive the equilibrium with the excess acid either sent to the
reaction or removed by distillation prior to sending the material
to the reactor. Such parameters may be adjusted to meet the needs
of the process. Such reactions are described in U.S. Pat. No.
7,179,873 which is incorporated by reference herein in its
entirety.
[0046] Generally, n=x, so that the metallic comonomer does not
contain any of the anionic ligand A. When this is the case, the
monoanionic ligands A are replaced by the acrylic acid upon contact
with the acrylate precursor, to form a metal acrylate. In an
alternate embodiment, x<n, and anionic ligand A is present in
the metallic comonomer. The A ligands, in these cases, are not
fully replaced, resulting in mixed-species type metallic comonomers
that contain a metal, an acrylate, and the anionic A ligand. Such
mixed-species type metallic comonomers include
Zr[O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(OBu).sub.2,
Zr[O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(OiPr).sub.2, and
Al[(O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(O.sup.iPr). Mixed
species such as
Al[(O.sub.2C(CH.sub.3).dbd.CH.sub.2].sub.2(O.sup.iPr), for example,
could impart different intermolecular binding energies between the
pseudo-networked materials altering the processing/property
balance.
[0047] The metal acrylate may be present in an amount effective to
impart one or more user-desired properties to the polystyrene
ionomer. For example, the metal acrylate may be present in the
polystyrene ionomer in an amount ranging from 0.01 to 50% weight
percent by total weight of the composition, alternatively from 0.01
wt. % to 25 wt. %, alternatively from 0.1 wt. % to 10 wt. %,
alternatively from 0.1 wt. % to 5 wt. %, alternatively from 0.1 wt.
% to 1 wt. %, alternatively from 0.01 wt. % to 1 wt. %. In an
embodiment, the amount of polystyrene present in the polystyrene
ionomer may range from 25 to 99.99% weight percent by total weight
of the polystyrene ionomer, alternatively from 25 wt. % to 95 wt.
%, alternatively from 50 wt. % to 90 wt. %, alternatively from 50
wt. % to 75 wt. %.
[0048] The term "ionomer" is used throughout the application to
refer to the copolymer of a styrenic monomer and metallic comonomer
that is networked or branched via ionic interactions. Thus, terms
such as "networked styrenic copolymer", "branched ionomer" and the
like describe the same polymer composition of the present invention
and can be used interchangeably with the term "polystyrene
ionomer." The styrenic monomer of the present invention can be
chosen from styrene, other vinylidene aromatic monomers, or
combinations thereof. Styrene monomer includes a variety of
substituted styrenes (e.g., alpha-methyl styrene), ring-substituted
styrenes such as p-methylstyrene as well as unsubstituted
styrenes.
[0049] The polystyrene ionomer can be formed in the presence of one
or more additional comonomers and/or elastomers. In an embodiment,
the polystyrene ionomer includes styrene and an elastomeric
material such that the resulting polymer is a high impact
polystyrene (HIPS). Such HIPS contains an elastomeric material that
is embedded in the styrenic polymer resulting in the composition
having an increased impact resistance. The elastomer can be derived
from a conjugated diene, such as 1,3-butadiene,
2-methyl-1,3-butadiene, 2 chloro-1,3 butadiene,
2-methyl-1,3-butadiene, and 2 chloro-1,3-butadiene. Alternatively,
the polystyrene ionomer can be HIPS having an elastomer derived
from an aliphatic conjugated diene monomer. Without limitation,
examples of suitable aliphatic conjugated diene monomers include
C.sub.4 to C.sub.9 dienes such as butadiene monomers. Blends or
copolymers of the diene monomers may also be used.
[0050] In an embodiment, the polystyrene ionomer is a terpolymer, a
copolymer, or a copolymer adduct. For example, the polystyrene
ionomer may be an acrylonitrile styrene butadiene (ABS) copolymer;
a free acid copolymer (PS/MA/HMA); or a styrene, metal acrylate,
free acrylic acid adduct (PS/MA.cndot.HMA).
[0051] In an embodiment, the polystyrene ionomer is ABS. ABS is a
class of thermoplastic terpolymers with usually more than about 50%
styrene and varying amounts of acrylonitrile and butadiene. The
three components are combined by using methods known to one of
ordinary skill in the art such as for example polymerization, graft
copolymerization, physical mixtures and combinations thereof.
[0052] Polystyrene ionomers of the present invention can be used in
many applications, such as extrusion, foaming, oriented sheet and
production, molding, and the like.
[0053] In one embodiment, the invention is a method for preparing a
metal acrylate that includes contacting a metal complex and a metal
acrylate precursor, both of the type described previously herein.
FIG. 1 is one embodiment of a mixing system that may be used for
contacting the metal complex and the acrylate precursor. Referring
to FIG. 1, a system 100 may have at least two vessels 110 and 120
that are in fluid communication with a mixing vessel 130 via
flowlines 115 and 125, respectively. Additionally, fluid pumps
and/or valves may be used to regulate the rate at which the
contents of both vessels 110 and 120 are fed into the mixing vessel
130. In an embodiment, the vessels 110 and 120 contain a metal
complex and a metal acrylate precursor, respectively.
[0054] The system 100 may include additional devices and mechanisms
to regulate conditions within the mixing vessel 130 such as
temperature controlling jackets, agitators, mixers, and the like
that may be coupled to the mixing vessel 130 to allow for a series
of user-desired conditions within the mixing vessel 130. Such
devices and mechanisms would be known to one of ordinary skill in
the art. The mixing vessel 130 may also be vented at a reduced
pressure or equipped with a condenser or a partial condenser to
remove unwanted byproducts that may be present or formed following
the contacting of the metal complex and metal acrylate precursor.
The metal acrylate precursor and metal complex may be contacted in
the mixing vessel 130 for a time period and under conditions
conducive to the formation of a metal acrylate. Such conditions may
vary depending on a number of factors such as the type and amount
of metal acrylate to be formed and may be determined
empirically.
[0055] In an embodiment, in situ formation of the metal acrylate
includes contacting the reagents described previously herein in a
mixing vessel of the type schematized in FIG. 1 to generate a metal
acrylate. The mixing vessel 130 may be in fluid communication with
one or more reaction zones such as to allow the metal acrylate
composition to enter a reaction zone where it may be employed for
the preparation of the polystyrene ionomer. Hereinafter the
reaction zone for preparation of the polystyrene ionomer will be
termed reaction zone 1. Reaction zone 1 may have one or more
reactors and will be described in more detail later herein. In an
embodiment, reaction zone 1 includes all devices located downstream
of mixing vessel 130 in FIG. 1. The components necessary for
preparing the metal acrylate may be contacted before or within a
mixing chamber that is in proximity to reaction zone 1.
[0056] In alternative embodiments, the metal complex and metal
acrylate precursor may be contacted within reaction zone 1. For
example, the metal acrylate precursor and metal complex may be
contacted in reaction zone 1 under conditions suitable for the
formation of the metal acrylate. The metal acrylate may then be
contacted with the styrenic polymer, optional elastomer, and other
components under conditions suitable for the preparation of the
polystyrene ionomer. Alternatively, the metal acrylate may be
prepared in one or more devices co-housed or co-attached to one or
more reaction zones wherein the metal acrylate is to be employed.
Alternatively, the metal acrylate may be prepared in close physical
proximity to the reaction zone wherein material is to be employed.
In some embodiments, in situ formation of the metal acrylate
involves contacting the components necessary to form a metal
acrylate within a reaction zone (e.g. polymerization vessel) in
order to form a metal acrylate during or immediately prior to the
use of the metal acrylate in a user desired process. Herein in situ
refers to preparation of the metal acrylate in close
temporal/physical proximity to a reaction zone (e.g., reaction zone
1), alternatively within the reaction zone, in which it is to be
employed.
[0057] The metal acrylate generated in the mixing vessel 130 may
function as a feed component to a downstream reactor. Referring to
FIG. 1, the metal acrylate generated in mixing vessel 130 may be
conveyed downstream via flowline 135 to a prepolymerization reactor
160. The prepolymerization reactor 160 may also receive additional
feed components (e.g. comonomer, catalyst, cocatalyst, etc) from
vessels 140 and 150 via flowlines 145 and 155, respectively. The
feed components from the mixing vessel 130 and the vessels 140 and
150 may be subject to conditions in the prepolymerization reactor
160 that allow for the polymerization of components of the feed to
reach a desired conversion. In an embodiment, the feed components
further include styrene monomer and the resultant polymer includes
polystyrene-metal acrylate. In an alternative embodiment, the feed
components further include styrene monomer and one or more
elastomers of the type described herein and the resultant product
is a HIPS-metal acrylate copolymer. As will be understood by one of
ordinary skill in the art, the reaction to produce the metal
acrylate will result in formation of additional materials that may
be removed prior to the entry of the metal acrylate into reaction
zone 1. Additional devices (e.g. filters, sorbents, etc.) may be
disposed downstream of the mixing vessel 130 and upstream of
reaction zone 1 (e.g., upstream of prepolymerization reactor 160)
so as to allow for purification of the metal acrylate composition
and removal of materials that may negatively impact the production
and/or quality of the polystyrene ionomer.
[0058] The effluent from the prepolymerization reactor 160 may be
conveyed to additional downstream reactor systems to further the
polymerization of the feed components as is known to one of
ordinary skill in the art and described in detail in the
literature. For example, the effluent from the prepolymerization
reactor 160 may be passed through a heating device into a
polymerization reactor 170 via flowline 165. Upon completion of the
polymerization reaction the effluent of the polymerization reactor
170, may be recovered and subsequently processed, for example
devolatized, pelletized, etc.
[0059] The system 100 may include additional devices such as
heaters, coolers, pumps, temperature/pressure controls, valves,
static mixers, vents, condenser, and the like as needed. The
polymerization process will be described in more detail later
herein.
[0060] Referring to FIG. 2, in an alternative embodiment, in situ
generation of a metal acrylate of the type described herein is
carried out using a mixing system 200. In such an embodiment, the
metal acrylate precursor (e.g., H-MA) may be mixed with styrene
monomer in one vessel 220 while styrene monomer and a metal complex
(e.g., Al(OiPr).sub.3) are in a second vessel 210. Feeds from the
two vessels may enter a downstream static mixer 230 wherein the
feeds are contacted to form a reaction mixture and subsequently
conveyed to a contacting vessel 240 which is in fluid communication
with the static mixer 230. For example, a first feed may contain
the styrene monomer and the acrylate precursor while a second feed
may contain the metal complex. The first and second feed may enter
a static mixer 230 before being conveyed to a contacting vessel
240. The reaction mixture may have a residence time in the
contacting vessel 240 sufficient to allow for in situ formation of
the metal acrylate. In an embodiment, the reaction mixture
residence time in the contacting vessel 240 ranges from 15 minutes
to 1 hour, alternatively from 20 minutes to 45 minutes,
alternatively 30 minutes. Following the residence time, the
reaction mixture may enter conduit 245 and be conveyed to one or
more downstream polymerization reactors 250.
[0061] The process for in situ formation of the metal acrylate as
described herein may reduce the need for handling fine metal
acrylate powders that offer challenges to large-scale production.
Additionally, the process allows a variety of materials to be
generated employing a single feed system that allows the properties
of the comonomer to be tailored to control the properties of the
final polymer. Further, the formation of the metal acrylate in situ
may allow for improved control of the ratio of acrylic acid to the
metal complex as well as the overall feed rate to the
polymerization unit thus, enabling both the class and overall
concentration of the in situ generated comonomer to be dictated by
the desired attributes of the final polystyrene ionomer.
[0062] In an embodiment, the polymerization reaction to form the
polystyrene ionomer may be carried out in a solution or mass
polymerization process. Mass polymerization, also known as bulk
polymerization, refers to the polymerization of a monomer in the
absence of any medium other than the monomer and a catalyst or
polymerization initiator. Solution polymerization refers to a
polymerization process in which the monomers and polymerization
initiators are dissolved in a non-monomeric liquid solvent at the
beginning of the polymerization reaction. The liquid is usually
also a solvent for the resulting polymer or copolymer.
[0063] The temperature ranges useful with the process of the
present disclosure can be selected to be consistent with the
operational characteristics of the equipment used to perform the
polymerization. In one embodiment, the temperature range for the
polymerization can be from 70.degree. C. to 240.degree. C. In
another embodiment, the temperature range for the polymerization
can be from 100.degree. C. to 180.degree. C. In yet another
embodiment, the polymerization reaction may be carried out in a
plurality of reactors with each reactor having an optimum
temperature range. For example, the polymerization reaction may be
carried out in a reactor system employing first and second
polymerization reactors that are either continuously stirred tank
reactors (CSTR) or plug-flow reactors. In an embodiment, a
polymerization reactor for the production of a polystyrene ionomer
of the type disclosed herein comprising a plurality of reactors may
have the first reactor (e.g. a CSTR), also known as the
prepolymerization reactor, operated in the temperature range of
from 70.degree. C. to 135.degree. C. while the second reactor (e.g.
CSTR or plug flow) may be operated in the range of from 100.degree.
C. to 165.degree. C.
EXAMPLE
[0064] The following example is meant to be merely illustrative of
a particular embodiment of the present invention, and is by no
means limiting of the scope of the invention.
[0065] In situ preparation of a metal acrylate of the type
described herein was investigated. Aluminum isopropoxide,
Al(O.sup.iPr).sub.3, and methacrylic acid, H-MA, were mixed in
different batches of styrene, which were then mixed en route to a
polymerization unit. Upon contact between these two chemicals, they
formed a comonomer (presumably, Al(MA).sub.3) that reacted with
styrene in a similar fashion as would ZnDMA. The experiment
consisted of three different conditions, where the primary variable
was the concentration of Al(MA).sub.3 feed to the unit. The three
concentration conditions were as follows: Trial A: 250 ppm
Al(MA).sub.3; Trial B: 500 ppm Al(MA).sub.3 ; and Trial C: 800 ppm
Al(MA).sub.3. The Al(OiPr).sub.3 and H-MA were mixed in different
batches of styrene, which were then mixed en route to the reactor.
An additive feed system for mixing of the styrene monomer
comprising either Al(OiPr).sub.3 or H-MA is depicted in FIG. 2
which was previously described herein. The aluminum content, color
(type, color L, color a, color b, yellowness index), Gel permeation
characteristics (GPC) (including number average molecular weight
(Mn), weight average molecular weight (Mw), size average molecular
weight (Mz), polydispersity, peak MW), melt flow, and melt strength
(force & velocity). These results are presented in Table 1. A
styrenic polymer commercially available from Total Petrochemicals
USA, Inc., CX5229, was used as the control resin. The color
measurements were made in accordance with ASTM D-1295.
TABLE-US-00001 TABLE 1 Sample Test Control Trial A Trial C Trial B
Aluminum XRF Aluminum content 0 ppm 4 ppm 6 ppm 28 ppm Color Sample
Type -- Chip Chip Chip Color L -- 80.4 80.1 78.6 Color a -- -2.09
-2.09 -2.13 Color b -- 2.56 2.86 3.29 Y1 -- 3.84 4.5 5.55 GPC
M.sub.n kg/mol 94.658 95.707 96.165 95.703 M.sub.w kg/mol 214.767
217.814 219.374 219.064 M.sub.z kg/mol 363.954 373.623 374.393
375.388 Polydispersity 2.269 2.275 2.281 2.289 Peak MW kg/mol
194.492 195.304 197.571 196.523 Melt flow MFR g/10 min 4.41 4.97
4.58 4.72 Melt strength Force 0.024N 0.016N 0.016N 0.016N Velocity
3.33 m/s 3.33 m/s 3.33 m/s 3.33 m/s
[0066] The melt strengths of the samples prepared in Trials A-C,
Control (CX5229), Total Petrochemicals 585 and Total Petrochemicals
535 are compared in FIGS. 3 and 4. Total Petrochemicals 585 is a
high molecular weight, low melt flow, high heat crystal grade
polystyrene and Total Petrochemicals 535 is a high heat crystal
polystyrene, both of which are commercially available from Total
Petrochemicals USA, Inc. The melt strengths were determined using
the hauloff method. The hauloff method measures the extensional
properties of polymer melts by dragging a vertical melt strand at a
constant pull-off speed with a linear or exponentially accelerating
velocity. The force needed to elongate the strand is used to
calculate the melt strength.
[0067] Referring to FIG. 3, the baseline condition for CX-5229
demonstrates there is an increase in melt strength over that of
Total Petrochemicals 535, putting the material closer to the melt
strength of Total Petrochemicals 585 while maintaining a higher
melt flow rate typically associated with Total Petrochemicals
535.
[0068] In contrast, as shown in FIG. 4, the samples from Trial A-C
displayed no appreciable increase in melt strength but the high
melt flow is maintained. Color and GPC were similar to those
observed with the control sample. Further, during reaction when
mixing the solution into the two separate feed pots a drastic
increase in temperature was noted, the pump head pressure spiked
indicating a plug somewhere along the feed line, and a color change
to the Al(OiPR).sub.3 and H-MA solutions was noted when placed in
the stainless steel feed vessels. Further additional experiments
having an increase in Al(OiPR).sub.3 and H-MA feed rate showed the
melt flow rate did not decrease as expected during online
testing.
[0069] FIG. 5 shows Mz and polydispersity as a function of aluminum
concentration, in ppm, for the three trial resins. As the figure
indicates, trials A-C show a trend of increased Mz and
polydispersity with increased concentration of the Aluminum metal
complex.
[0070] As used herein, the term "acrylate" can include related
compounds such as a methacrylate.
[0071] As used herein, the term "ionomer" refers to a copolymer
comprising as ionic comonomer that provides reversible
networking/branching to the polymer composition.
[0072] As used herein, the term "metallic comonomer" refers to a
comonomer for preparing an ionomer that contains a metal ion.
[0073] Herein in situ refers to preparation of a metallic comonomer
in close temporal/physical proximity to a reaction zone,
alternatively within the reaction zone, in which it is to be
employed.
[0074] The various embodiments of the present invention can be
joined in combination with other embodiments of the invention and
the listed embodiments herein are not meant to limit the invention.
All combinations of various embodiments of the invention are
enabled, even if not given in a particular example herein.
[0075] While illustrative embodiments have been depicted and
described, modifications thereof can be made by one skilled in the
art without departing from the spirit and scope of the disclosure.
Where numerical ranges or limitations are expressly stated, such
express ranges or limitations should be understood to include
iterative ranges or limitations of like magnitude falling within
the expressly stated ranges or limitations (e.g., from about 1 to
about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11,
0.12, 0.13, etc.).
[0076] Depending on the context, all references herein to the
"invention" may in some cases refer to certain specific embodiments
only. In other cases it may refer to subject matter recited in one
or more, but not necessarily all, of the claims. While the
foregoing is directed to embodiments, versions and examples of the
present invention, which are included to enable a person of
ordinary skill in the art to make and use the inventions when the
information in this patent is combined with available information
and technology, the inventions are not limited to only these
particular embodiments, versions and examples. Other and further
embodiments, versions and examples of the invention may be devised
without departing from the basic scope thereof and the scope
thereof is determined by the claims that follow.
* * * * *