PATENT
Methods for terminating olefin polymerizations
(Chevron Phillips Chemical Company LP)
United
States Patent 8440772
Inventors:
Yang, Qing (Bartlesville, OK, US)
Mcdaniel, Max P. (Bartlesville, OK, US)
Crain, Tony R. (Niotaze, KS, US)
Collins, Kathy S. (Bartlesville, OK, US)
Application Number:
13/096142
Publication Date:
05/14/2013
Assignee:
Chevron Phillips Chemical Company LP (The Woodlands, TX, US)
Abstract:
Catalyst deactivating agents and compositions
containing catalyst deactivating agents are disclosed. These catalyst
deactivating agents can be used in methods of controlling polymerization
reactions, methods of terminating polymerization reactions, methods of
operating polymerization reactors, and methods of transitioning between
catalyst systems.
BACKGROUND
OF THE INVENTION
There are various methods and materials that can be employed to terminate a
polymerization reaction. For example, injections of large amounts of water or
isopropanol into a polymerization reactor or downstream of the reactor can be
used to terminate the polymerization reaction. However, these methods and
materials often can lead to excessive cost, clean-up, and/or downtime.
It would be beneficial to develop new methods and materials that can
effectively terminate a polymerization reaction, either for rapid termination
in the polymerization reactor due to a process upset, or for neutralization of
catalyst reactivity downstream of the reactor during normal polymer production,
yet reduce the associated cost, clean-up, and downtime. Accordingly, it is to
these ends that the present disclosure is directed.
SUMMARY OF THE INVENTION
Methods of controlling a polymerization reaction in a polymerization reactor
system are disclosed herein. One such method can comprise introducing a catalyst
deactivating agent into the polymerization reactor system to partially or
completely terminate the polymerization reaction. The catalyst deactivating
agent can be introduced into a polymerization reactor within the polymerization
reactor system, and/or the catalyst deactivating agent can be introduced
downstream of the polymerization reactor. Consistent with embodiments disclosed
herein, the catalyst deactivating agent can comprise a polyethylene glycol, a
polypropylene glycol, a compound having formula (I), or a combination thereof,
wherein formula (I) is:
R1—X1—R3—X2—R2 (I).
In formula (I),
X1 and X2 independently can be O, S, or NR, wherein R can
be hydrogen or a C1 to C18 hydrocarbyl group;
R1 and R2 independently can be hydrogen or a C1 to
C18 hydrocarbyl group; and
R3 can comprise up to 18 carbon atoms and can be
(i) a substituted or unsubstituted chain of at least two contiguous carbons
atoms, one end of which is bonded to X1 and the other end of which
is bonded to X2, or
(ii) a substituted or unsubstituted ether, thioether, or amine group having at
least four carbon atoms, a two-carbon atom end of which is bonded to X1 and
the other two-carbon atom end of which is bonded to X2.
Another method of controlling a polymerization reaction in a polymerization
reactor system is provided, and in this embodiment, the method can comprise:
(i) introducing a transition metal-based catalyst system, an olefin monomer,
and optionally an olefin comonomer into a polymerization reactor within the
polymerization reactor system;
(ii) contacting the transition metal-based catalyst system with the olefin
monomer and the optional olefin comonomer under polymerization conditions to
produce an olefin polymer; and
(iii) introducing a catalyst deactivating agent into the polymerization reactor
to partially or completely terminate the polymerization reaction in the
polymerization reactor.
Another method of controlling a polymerization reaction in a polymerization
reactor system is provided, and in this embodiment, the method can comprise:
(1) introducing a transition metal-based catalyst system, an olefin monomer,
and optionally an olefin comonomer into a polymerization reactor within the
polymerization reactor system;
(2) contacting the transition metal-based catalyst system with the olefin
monomer and the optional olefin comonomer under polymerization conditions to
produce an olefin polymer; and
(3) introducing a catalyst deactivating agent into the polymerization reactor
system downstream of the polymerization reactor to completely terminate the
polymerization reaction.
Another method of controlling a polymerization reaction in a polymerization
reactor system is provided herein, and this method can comprise:
(a) introducing a transition metal-based catalyst system, an olefin monomer,
and optionally an olefin comonomer into a polymerization reactor within the
polymerization reactor system;
(b) contacting the transition metal-based catalyst system with the olefin
monomer and the optional olefin comonomer under polymerization conditions to
produce an olefin polymer;
(c) monitoring a process variable to detect an undesired condition in the
polymerization reactor system; and
(d) when the undesired reaction condition has reached a predetermined critical
level, introducing a catalyst deactivating agent into the polymerization
reactor.
Yet, in another embodiment, a method of controlling a polymerization reaction
in a polymerization reactor system directed to transitioning between catalyst
systems is provided. This method can comprise:
(A) introducing a first transition metal-based catalyst system, a first olefin
monomer, and optionally a first olefin comonomer into a polymerization reactor
in the polymerization reactor system;
(B) contacting the first transition metal-based catalyst system with the first
olefin monomer and the optional first olefin comonomer under polymerization
conditions to produce a first olefin polymer;
(C) discontinuing the introducing of the first transition metal-based catalyst
system into the polymerization reactor before, during, or after a step of
introducing a catalyst deactivating agent into the polymerization reactor; and
(D) introducing a second transition metal-based catalyst system into the
polymerization reactor and contacting the second transition metal-based
catalyst system with a second olefin monomer and optionally a second olefin
comonomer under polymerization conditions to produce a second olefin polymer.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 presents a plot of the reaction rate versus the reaction time for
Example 1 at a DPGME/Cr molar ratio of 0.035:1.
FIG. 2 presents a plot of the reaction rate versus the reaction time for
Example 2 at a DPGME/Cr molar ratio of 0.1:1.
FIG. 3 presents a plot of the reaction rate versus the reaction time for
Example 3 at a DPGME/Cr molar ratio of 0.2:1.
FIG. 4 presents a plot of the reaction rate versus the reaction time for
Example 6 at a DPGME/Cr molar ratio of 0.8:1.
FIG. 5 presents a plot of the reaction rates versus the reaction times for
Examples 18-22 at DPGME/Ti molar ratios up to 8.4:1.
FIG. 6 presents the data of FIG. 5, but the molar ratios listed are based on
the moles of Al in the alkylaluminum component of the catalyst system, instead
of on the moles of Ti.
FIG. 7 presents a plot of the reaction rates versus the reaction times for
Example 23-25 at DPGME/Al molar ratios in a range from 0.33:1 to 0.55:1.
FIG. 8 presents a plot of the reaction rates versus the reaction times for
Example 26-28 at DME/Al molar ratios in a range from 0.19:1 to 0.76:1.
DEFINITIONS
To define more clearly the terms used herein, the following definitions are
provided. Unless otherwise indicated, the following definitions are applicable
to this disclosure. If a term is used in this disclosure but is not
specifically defined herein, the definition from the IUPAC Compendium of
Chemical Terminology, 2nd Ed (1997) can be applied, as long as that
definition does not conflict with any other disclosure or definition applied
herein, or render indefinite or non-enabled any claim to which that definition
is applied. To the extent that any definition or usage provided by any document
incorporated herein by reference conflicts with the definition or usage
provided herein, the definition or usage provided herein controls.
Regarding claim transitional terms or phrases, the transitional term
“comprising,” which is synonymous with “including,” “containing,” “having,” or
“characterized by,” is inclusive or open-ended and does not exclude additional,
unrecited elements or method steps. The transitional phrase “consisting of”
excludes any element, step, or ingredient not specified in the claim. The
transitional phrase “consisting essentially of” limits the scope of a claim to
the specified materials or steps and those that do not materially affect the basic
and novel characteristic(s) of the claim. A “consisting essentially of” claim
occupies a middle ground between closed claims that are written in a
“consisting of” format and fully open claims that are drafted in a “comprising”
format. Absent an indication to the contrary, describing a compound or
composition as “consisting essentially of” is not to be construed as
“comprising,” but is intended to describe the recited component that includes
materials which do not significantly alter the composition or method to which
the term is applied. For example, a feedstock consisting essentially of a
material A can include impurities typically present in a commercially produced
or commercially available sample of the recited compound or composition. When a
claim includes different features and/or feature classes (for example, a method
step, feedstock features, and/or product features, among other possibilities),
the transitional terms comprising, consisting essentially of, and consisting of
apply only to the feature class to which it is utilized, and it is possible to
have different transitional terms or phrases utilized with different features
within a claim. For example, a method can comprise several recited steps (and
other non-recited steps), but utilize a system preparation consisting of
specific components; alternatively, consisting essentially of specific
components; or alternatively, comprising the specific components and other
non-recited components.
While compositions and methods are often described in terms of “comprising”
various components or steps, the compositions and methods can also “consist
essentially of” or “consist of” the various components or steps, unless stated
otherwise.
The terms “a,” “an,” and “the” are intended to include plural alternatives,
e.g., at least one. For instance, the disclosure of “a catalyst deactivating
agent,” “an olefin comonomer,” etc., is meant to encompass one, or mixtures or
combinations of more than one, catalyst deactivating agent, olefin comonomer,
etc., unless otherwise specified.
For any particular compound or group disclosed herein, any name or structure
(general or specific) presented is intended to encompass all conformational
isomers, regioisomers, stereoisomers, and mixtures thereof that can arise from
a particular set of substituents, unless otherwise specified. The name or
structure (general or specific) also encompasses all enantiomers,
diastereomers, and other optical isomers (if there are any) whether in
enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would
be recognized by a skilled artisan, unless otherwise specified. A general
reference to pentane, for example, includes n-pentane, 2-methyl-butane, and
2,2-dimethylpropane; and a general reference to a butyl group includes a
n-butyl group, a sec-butyl group, an iso-butyl group, and a t-butyl group.
Within this disclosure, the normal rules of organic nomenclature will prevail.
For instance, when referencing substituted compounds or groups, references to
substitution patterns are taken to indicate that the indicated group(s) is(are)
located at the indicated position and that all other non-indicated positions
are hydrogen. For example, reference to a 4-substituted phenyl group indicates
that there is a non-hydrogen substituent located at the 4 position and
hydrogens located at the 2, 3, 5, and 6 positions. By way of another example,
reference to a 3-substituted naphth-2-yl indicates that there is a non-hydrogen
substituent located at the 3 position and hydrogens located at the 1, 4, 5, 6,
7, and 8 positions. References to compounds or groups having substitutions at
positions in addition to the indicated position will be referenced using
comprising or some other alternative language. For example, a reference to a
phenyl group comprising a substituent at the 4 position refers to a phenyl
group having a substituent at the 4 position and hydrogen or any non-hydrogen
substituent at the 2, 3, 5, and 6 positions.
In one embodiment, a chemical “group” can be defined or described according to
how that group is formally derived from a reference or “parent” compound, for
example, by the number of hydrogen atoms removed from the parent compound to
generate the group, even if that group is not literally synthesized in such a
manner. These groups can be utilized as substituents or coordinated or bonded
to metal atoms. By way of example, an “alkyl group” formally can be derived by
removing one hydrogen atom from an alkane, while an “alkylene group” formally
can be derived by removing two hydrogen atoms from an alkane. Moreover, a more
general term can be used to encompass a variety of groups that formally are
derived by removing any number (“one or more”) hydrogen atoms from a parent
compound, which in this example can be described as an “alkane group,” and which
encompasses an “alkyl group,” an “alkylene group,” and materials having three
or more hydrogen atoms, as necessary for the situation, removed from an alkane.
The disclosure that a substituent, ligand, or other chemical moiety can
constitute a particular “group” implies that the well-known rules of chemical
structure and bonding are followed when that group is employed as described.
When describing a group as being “derived by,” “derived from,” “formed by,” or
“formed from,” such terms are used in a formal sense and are not intended to
reflect any specific synthetic methods or procedures, unless specified
otherwise or the context requires otherwise.
Also, unless otherwise specified, any carbon-containing group for which the
number of carbon atoms is not specified can have, according to proper chemical
practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18
carbon atoms, or any range or combination of ranges between these values. For
example, unless otherwise specified, any carbon-containing group can have from
1 to 18 carbon atoms, from 1 to 15 carbon atoms, from 1 to 12 carbon atoms,
from 1 to 10 carbon atoms, from 1 to 8 carbon atoms, or from 1 to 5 carbon
atoms, and the like. Moreover, other identifiers or qualifying terms can be
utilized to indicate the presence of, or absence of, a particular substituent,
a particular regiochemistry, and/or stereochemistry, or the presence of absence
of a branched underlying structure or backbone. Any specific carbon-containing
group is limited according to the chemical and structural requirements for that
specific group, as understood by one of ordinary skill. For example, unless
otherwise specified, an aryl group can have from 6 to 18 carbon atoms, from 6
to 15 carbon atoms, from 6 to 12 carbon atoms, or from 6 to 10 carbon atoms,
and the like. Thus, according to proper chemical practice and unless otherwise
specified, an aryl group can have 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,
or 18 carbon atoms, or any range or combination of ranges between these values.
Other numerical ranges are disclosed herein. When Applicants disclose or claim
a range of any type, Applicants' intent is to disclose or claim individually
each possible number that such a range could reasonably encompass, including
end points of the range as well as any sub-ranges and combinations of
sub-ranges encompassed therein, unless otherwise specified. As a representative
example, Applicants disclose that a molar ratio of a catalyst deactivating
agent to a transition metal in a transition metal-based catalyst system can be
in a range from 0.01:1 to 10:1 in certain embodiments. By a disclosure that the
molar ratio of the catalyst deactivating agent to the transition metal in the
transition metal-based catalyst system can be in a range from 0.01:1 to 10:1,
Applicants intend to recite that the molar ratio can be 0.01:1, about 0.02:1,
about 0.03:1, about 0.04:1, about 0.05:1, about 0.06:1, about 0.07:1, about
0.08:1, about 0.09:1, about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1, about
0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, about 1:1, about
1.5:1, about 2:1, about 2.5:1, about 3:1, about 3.5:1, about 4:1, about 4.5:1,
about 5:1, about 5.5:1, about 6:1, about 6.5:1, about 7:1, about 7.5:1 about
8:1, about 8.5:1 about 9:1, about 9.5:1, or 10:1. Additionally, the molar ratio
can be within any range from 0.01:1 to 10:1 (for example, the molar ratio can
be in a range from about 0.02:1 to about 2:1), and this also includes any
combination of ranges between 0.01:1 and 10:1. Likewise, all other ranges
disclosed herein should be interpreted in a manner similar to these examples.
Applicants reserve the right to proviso out or exclude any individual members
of any such group, including any sub-ranges or combinations of sub-ranges
within the group, that can be claimed according to a range or in any similar
manner, if for any reason Applicants choose to claim less than the full measure
of the disclosure, for example, to account for a reference that Applicants can
be unaware of at the time of the filing of the application. Further, Applicants
reserve the right to proviso out or exclude any individual substituents,
analogs, compounds, ligands, structures, or groups thereof, or any members of a
claimed group, if for any reason Applicants choose to claim less than the full
measure of the disclosure, for example, to account for a reference that
Applicants can be unaware of at the time of the filing of the application.
The term “substituted” when used to describe a group or a chain of carbon atoms,
for example, when referring to a substituted analog of a particular group or
chain, is intended to describe or group or chain wherein any non-hydrogen
moiety formally replaces a hydrogen in that group or chain, and is intended to
be non-limiting. A group or chain also can be referred to herein as
“unsubstituted” or by equivalent terms such as “non-substituted,” which refers
to the original group or chain. “Substituted” is intended to be non-limiting
and can include hydrocarbon substituents as specified and as understood by one
of ordinary skill in the art.
The term “hydrocarbon” whenever used in this specification and claims refers to
a compound containing only carbon and hydrogen. Other identifiers can be
utilized to indicate the presence of particular groups in the hydrocarbon
(e.g., halogenated hydrocarbon indicates the presence of one or more halogen
atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The
term “hydrocarbyl group” is used herein in accordance with the definition specified
by IUPAC: a univalent group formed by removing a hydrogen atom from a
hydrocarbon (that is, a group containing only carbon and hydrogen). Similarly,
a “hydrocarbylene group” refers to a group formed by removing two hydrogen
atoms from a hydrocarbon, either two hydrogen atoms from one carbon atom or one
hydrogen atom from each of two different carbon atoms. Therefore, in accordance
with the terminology used herein, a “hydrocarbon group” refers to a generalized
group formed by removing one or more hydrogen atoms (as needed for the
particular group) from a hydrocarbon. A “hydrocarbyl group,” “hydrocarbylene
group,” and “hydrocarbon group” can be acyclic or cyclic groups, and/or can be
linear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and
“hydrocarbon group” can include rings, ring systems, aromatic rings, and
aromatic ring systems, which contain only carbon and hydrogen. “Hydrocarbyl
groups,” “hydrocarbylene groups,” and “hydrocarbon groups” include, by way of
example, aryl, arylene, arene groups, alkyl, alkylene, alkane groups,
cycloalkyl, cycloalkylene, cycloalkane groups, aralkyl, aralkylene, and
aralkane groups, respectively, among other groups as members.
An aliphatic compound is a non-aromatic organic compound. An “aliphatic group”
is a generalized group formed by removing one or more hydrogen atoms (as needed
for the particular group) from the carbon atoms of an aliphatic compound. An
aliphatic compound can be acyclic or cyclic, saturated or unsaturated, and/or
linear or branched organic compound. Aliphatic compounds and aliphatic groups
can contain organic functional group(s) and/or atom(s) other than carbon and
hydrogen unless otherwise specified (e.g., an aliphatic hydrocarbon).
The term “alkane” whenever used in this specification and claims refers to a
saturated hydrocarbon compound. Other identifiers can be utilized to indicate
the presence of particular groups in the alkane (e.g., halogenated alkane
indicates the presence of one or more halogen atoms replacing an equivalent number
of hydrogen atoms in the alkane). The term “alkyl group” is used herein in
accordance with the definition specified by IUPAC: a univalent group formed by
removing a hydrogen atom from an alkane. An “alkane group” is a general term
that refers to a group formed by removing one or more hydrogen atoms (as needed
for the particular group) from an alkane. An “alkyl group” and “alkane group”
can be linear or branched unless otherwise specified. Primary, secondary, and
tertiary alkyl groups can be derived by removal of a hydrogen atom from a
primary, secondary, and tertiary carbon atom, respectively, of an alkane. The
n-alkyl group can be derived by removal of a hydrogen atom from a terminal
carbon atom of a linear alkane. The groups RCH2 (R≠H), R2CH(R≠H),
and R3C(R≠H) are primary, secondary, and tertiary alkyl groups,
respectively. The carbon atom by which indicated moiety is attached is a
secondary, tertiary, and quaternary carbon atom, respectively.
A cycloalkane is a saturated cyclic hydrocarbon, with or without side chains
(e.g., cyclobutane or methylcyclobutane). Unsaturated cyclic hydrocarbons
having at least one non-aromatic endocyclic carbon-carbon double or one triple
bond are cycloalkenes and cycloalkynes, respectively. Unsaturated cyclic
hydrocarbons having more than one such multiple bond can further specify the
number and/or position(s) of such multiple bonds (e.g., cycloalkadienes,
cycloalkatrienes, and so forth). The unsaturated cyclic hydrocarbons can be
further identified by the position of the carbon-carbon multiple bond(s).
A “cycloalkyl group” is a univalent group derived by removing a hydrogen atom
from a ring carbon atom from a cycloalkane. For example, a 1-methylcyclopropyl
group and a 2-methylcyclopropyl group are illustrated as follows:
A “cycloalkylene group” refers to a group derived by removing two hydrogen
atoms from a cycloalkane, at least one of which is a ring carbon. Thus, a
“cycloalkylene group” includes a group derived from a cycloalkane in which two
hydrogen atoms are formally removed from the same ring carbon, a group derived
from a cycloalkane in which two hydrogen atoms are formally removed from two
different ring carbons, and a group derived from a cycloalkane in which a first
hydrogen atom is formally removed from a ring carbon and a second hydrogen atom
is formally removed from a carbon atom that is not a ring carbon. A
“cycloalkane group” refers to a generalized group formed by removing one or
more hydrogen atoms (as necessary for the particular group and at least one of which
is a ring carbon) from a cycloalkane.
The term “alkene” whenever used in this specification and claims refers to a
compound that has at least one non-aromatic carbon-carbon double bond. The term
“alkene” includes aliphatic or aromatic, cyclic or acyclic, and/or linear and
branched alkenes unless expressly stated otherwise. Alkenes can also be further
identified by the position of the carbon-carbon double bond. Alkenes having
more than one such multiple bond are alkadienes, alkatrienes, and so forth. The
alkene can be further identified by the position(s) of the carbon-carbon double
bond(s).
An “alkenyl group” is a univalent group derived from an alkene by removal of a
hydrogen atom from any carbon atom of the alkene. Thus, “alkenyl group”
includes groups in which the hydrogen atom is formally removed from an sp2
hybridized (olefinic) carbon atom and groups in which the hydrogen atom
is formally removed from any other carbon atom. For example and unless
otherwise specified, propen-1-yl (—CH═CHCH3), propen-2-yl [(CH3)C═CH2],
and propen-3-yl (—CH2CH═CH2) groups are all encompassed
with the term “alkenyl group.” Similarly, an “alkenylene group” refers to a
group formed by formally removing two hydrogen atoms from an alkene, either two
hydrogen atoms from one carbon atom or one hydrogen atom from two different
carbon atoms. An “alkene group” refers to a generalized group formed by
removing one or more hydrogen atoms (as needed for the particular group) from
an alkene. When the hydrogen atom is removed from a carbon atom participating
in a carbon-carbon double bond, the regiochemistry of the carbon from which the
hydrogen atom is removed, and regiochemistry of the carbon-carbon double bond
can both be specified. Alkenyl groups can also have more than one such multiple
bond. The alkene group can also be further identified by the position(s) of the
carbon-carbon double bond(s).
The term “alkyne” is used in this specification and claims to refer to a
compound that has at least one carbon-carbon triple bond. The term “alkyne”
includes aliphatic or aromatic, cyclic or acyclic, and/or linear and branched
alkynes unless expressly stated otherwise. Alkynes having more than one such
multiple bond are alkadiynes, alkatriynes, and so forth. The alkyne group can
also be further identified by the position(s) of the carbon-carbon triple bond(s).
An “alkynyl group” is a univalent group derived from an alkyne by removal of a
hydrogen atom from any carbon atom of the alkyne. Thus, “alkynyl group”
includes groups in which the hydrogen atom is formally removed from an sp
hybridized (acetylenic) carbon atom and groups in which the hydrogen atom is
formally removed from any other carbon atom. For example and unless otherwise
specified, 1-propyn-1-yl (—C≡CCH3) and propyn-3-yl (HC≡CCH2—)
groups are encompassed with the term “alkynyl group.” Similarly, an “alkynylene
group” refers to a group formed by formally removing two hydrogen atoms from an
alkyne, either two hydrogen atoms from one carbon atom if possible or one
hydrogen atom from two different carbon atoms. An “alkyne group” refers to a
generalized group formed by removing one or more hydrogen atoms (as needed for
the particular group) from an alkyne. Alkyne groups can have more than one such
multiple bond. Alkyne groups can also be further identified by the position(s)
of the carbon-carbon triple bond(s).
An “aromatic group” refers to a generalized group formed by removing one or
more hydrogen atoms (as needed for the particular group and at least one of
which is an aromatic ring carbon atom) from an aromatic compound. Thus, an
“aromatic group” as used herein refers to a group derived by removing one or
more hydrogen atoms from an aromatic compound, that is, a compound containing a
cyclically conjugated hydrocarbon that follows the Hückel (4n+2) rule and
containing (4n+2) pi-electrons, where n is an integer from 1 to about 5.
Aromatic compounds and hence “aromatic groups” can be monocyclic or polycyclic
unless otherwise specified. Aromatic compounds include “arenes” (hydrocarbon
aromatic compounds), examples of which can include, but are not limited to,
benzene, naphthalene, and toluene, among others. As disclosed herein, the term
“substituted” can be used to describe an aromatic group wherein any
non-hydrogen moiety formally replaces a hydrogen in that group, and is intended
to be non-limiting.
An “aryl group” refers to a generalized group formed by removing a hydrogen
atom from an aromatic hydrocarbon ring carbon atom from an arene. One example
of an “aryl group” is ortho-tolyl (o-tolyl), the structure of which is shown
here.
Similarly, an “arylene group” refers to a group formed by removing two hydrogen
atoms (at least one of which is from an aromatic hydrocarbon ring carbon) from
an arene. An “arene group” refers to a generalized group formed by removing one
or more hydrogen atoms (as needed for the particular group and at least one of
which is an aromatic hydrocarbon ring carbon) from an arene.
An “aralkyl group” is an aryl-substituted alkyl group having a free valance at
a non-aromatic carbon atom, for example, a benzyl group is an “aralkyl” group.
Similarly, an “aralkylene group” is an aryl-substituted alkylene group having
two free valances at a single non-aromatic carbon atom or a free valence at two
non-aromatic carbon atoms while an “aralkane group” is a generalized is an
aryl-substituted alkane group having one or more free valances at a
non-aromatic carbon atom(s).
The term “polymer” is used herein generically to include olefin homopolymers,
copolymers, terpolymers, and so forth. A copolymer can be derived from an
olefin monomer and one olefin comonomer, while a terpolymer can be derived from
an olefin monomer and two olefin comonomers. Accordingly, “polymer” encompasses
copolymers, terpolymers, etc., derived from any olefin monomer and comonomer(s)
disclosed herein. Similarly, an ethylene polymer would include ethylene
homopolymers, ethylene copolymers, ethylene terpolymers, and the like. As an
example, an olefin copolymer, such as an ethylene copolymer, can be derived
from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the
monomer and comonomer were ethylene and 1-hexene, respectively, the resulting
polymer could be categorized an as ethylene/1-hexene copolymer. The term
“polymer” also is meant to include all molecular weight polymers, and is
inclusive of lower molecular weight polymers or oligomers. Applicants intend
for the term “polymer” to encompass oligomers derived from any olefin monomer
disclosed herein (as well from an olefin monomer and one olefin comonomer, an
olefin monomer and two olefin comonomers, and so forth).
In like manner, the scope of the term “polymerization” includes
homopolymerization, copolymerization, terpolymerization, etc., as well as
processes that might also be referred to as oligomerization processes.
Therefore, a copolymerization process would involve contacting an olefin
monomer (e.g., ethylene) and an olefin comonomer (e.g., 1-hexene) to produce an
olefin copolymer.
The terms “contact product,” “contacting,” and the like, are used herein to
describe compositions wherein the components are contacted together in any
order, in any manner, and for any length of time. For example, the components
can be contacted by blending or mixing. Further, unless otherwise specified,
the contacting of any component can occur in the presence or absence of any
other component of the compositions described herein. Combining additional
materials or components can be done by any suitable method. Further, the term
“contact product” includes mixtures, blends, solutions, slurries, reaction
products, and the like, or combinations thereof. Although “contact product”
can, and often does, include reaction products, it is not required for the
respective components to react with one another. Likewise, “contacting” two or
more components can result in a reaction product or a reaction mixture.
Consequently, depending upon the circumstances, a “contact product” can be a
mixture, a reaction mixture, or a reaction product.
Although any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the invention, the typical
methods and materials are herein described.
All publications and patents mentioned herein are incorporated herein by
reference for the purpose of describing and disclosing, for example, the
constructs and methodologies that are described in the publications, which
might be used in connection with the presently described invention. The
publications discussed throughout the text are provided solely for their
disclosure prior to the filing date of the present application. Nothing herein
is to be construed as an admission that the inventors are not entitled to
antedate such disclosure by virtue of prior invention.
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Showing posts with label CHEVRON. Show all posts
Friday, November 15, 2013
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
PATENT
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
United States Patent Application 20130150539
Inventors:
Stokes, Casey D. (Belle Chasse, LA, US)
Storey, Robson F. (Hattiesburg, MS, US)
Harrison, James J. (Novato, CA, US)
Application Number:
13/765563
Publication Date:
06/13/2013
Assignee:
The University Of Southern Mississippi (Hattiesburg, Ms, Us)
Chevron Oronite Company Llc (San Ramon, Ca, Us)
Abstract:
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds attached to the ring.
FIELD OF THE INVENTION
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring.
BACKGROUND OF THE INVENTION
Linear polyolefins made using a mono-functional initiator containing a single “exo-olefin”, “1,1-di-substituted” olefin, or “methylvinylidene,” end group are useful precursors for the preparation of polymers containing specific functional end groups. Polymers made using multi-functional initiators would have multiple exo-olefinic end groups. Polymers containing specific end groups are useful as lubricating oil additives. One example of a functionalized polymer containing hetero atoms is polyisobutenylsuccinic anhydride. Functional end groups may also be desirable for making polymers with potential for further reactions.
Conventional ionic polymerizations can be anionic or cationic. Anionic polymerizations proceed, in the presence of a base, through carbanions and favor monomers having electron withdrawing groups. Cationic polymerizations proceed, in the presence of an acid, through a carbocation, also called a carbenium ion, and favor monomers that have electron releasing groups.
Similarly to the conventional polymerization systems, living polymerization systems may be either anionic or cationic. The difference between conventional polymerizations and living polymerizations is that an ideal living polymerization proceeds in the absence of chain transfer and chain termination. Living polymerization systems are of great commercial importance because the degree of polymerization may be controlled by controlling the feed ratio of monomer to initiator and sequential addition of two or more different monomers affords the ability to produce block copolymers. Polymerization continues until the monomer is exhausted, but the polymers retain their ability to add additional monomers any time in the future. A number of such systems are well known in the art.
A further development is the cationic quasi-living polymerization systems using conventional monomers. Quasi-living polymerization requires certain restrictive conditions, for example anhydrous reagents. Cationic quasi-living polymerizations differ from truly living polymerizations in that, although the rate of chain transfer approaches zero, chain termination is present but reversible. One important example of a cationic quasi-living polymerization is the cationic quasi-living polymerization of isobutylene.
Typically, cationic quasi-living polymerizations of isobutylene yield narrow molecular weight distribution and one major polymer product containing the 2-chloro-2-methylpropyl end group, also referred to as the “tert-chloride” end group. Under certain conditions minor amounts of olefinic isomers may also be produced.
On the other hand, there are two major olefinic isomers produced during conventional polymerization of isobutylene with BF3, for example, the highly reactive exo-olefin isomer and the relatively unreactive 2-methyl-1-propenyl isomer, also referred to as the “tri-substituted” isomer or “endo olefin” isomer. Furthermore, conventional polymerizations of isobutylene yield polymers with broad molecular weight distributions or polydispersity indices.
Exclusive production of the exo-olefin isomer has not been previously achieved under conventional polymerization conditions.
There are two established methods for producing polyisobutylene containing only the exo-olefin end group. One method involves chemical dehydrohalogenation of tert-chloride terminated polyisobutylene using potassium tert-butoxide in a post polymerization reaction (U.S. Pat. No. 4,342,849). The other method involves in situ quenching of quasi-living isobutylene with methallyltrimethylsilane, which converts an active, living carbenium ion to the exo-olefin end group. (M. Roth and H. Mayr, Macromolecules, 29, 6104, 1996)
Polyisobutylene polymers containing more than one exo-olefin end group may be prepared using the above methods by the use of a multi-functional initiator.
The preparation of polyolefins, including polyisobutylene polymers, is well known in the art. A number of patents have discussed processes for making polyisobutylene polymers containing exo-olefin end groups, but none using quenching a cationic quasi-living polymerization system with one or more nitrogen-containing five-membered aromatic ring compounds.
European Patent No. 341012 discloses a method for producing polymers with narrow molecular weight distribution, where the ratio of the weight average molecular weight, M(w), to the number average molecular weight, M(n), approaches 1.
U.S. Pat. No. 4,152,499 discloses isobutylene polymers having a mean degree of polymerization from 10 to 100 and where the proportion of theoretically possible terminal double bonds is greater than in products prepared using aluminum trichloride. The patent also discloses the method of making the isobutylene polymers using boron trifluoride as the initiator.
U.S. Pat. No. 4,342,849 discloses the synthesis of polyisobutylene carrying either unsaturation or hydroxyl groups at both ends, in the case of a linear polymer, or at all ends in the case of a star polymer. The method involves the steps of refluxing a solution of telechelic di-halogen polyisobutylene, adding a solution strong base such as potassium t-butoxide and stirring to form the telechelic di-olefin polyisobutylene.
U.S. Pat. No. 4,393,199 discloses a method for carrying out cationic polymerization with molecular weight control in which a pre-initiator and a catalyst effective for cationic polymerization are mixed with a monomer. The resulting living polymer is then treated as desired.
U.S. Pat. No. 4,758,631 discloses a method of preparing allyl-terminated polyisobutylene by allylation with allyltrimethylsilane of tertiary chloro-capped polyisobutylene by electrophilic substitution. The synthesis begins with the boron trichloride catalyzed mono- or oligo-tertiary chloride “inifer” initiated polymerization of isobutylene, followed in the same reaction vessel by the addition of hexane, allyltrimethylsilane and titanium tetrachloride.
U.S. Pat. Nos. 4,910,321 and 5,122,572 disclose a catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. Nos. 4,929,683 and 5,066,730 disclose a catalyst composed of a complex of an organic ether and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. No. 5,219,948 discloses a method for preparing elastomeric polymers comprising alpha-olefins or conjugated alkadienes by cationic polymerization in the presence of titanium tetrachloride and an electron pair donor selected from pyridine or a non-hindered alkylpyridine. The polymers have very narrow, mono-modal molecular weight distribution.
U.S. Pat. No. 5,336,745 discloses a method for the direct synthesis of polymeric materials functionalized with desirable nitrogen-containing functional groups such as terminal azido, cyano, carbonylamino or thiocarbonylamino groups. Polymerization and functionalization occur in a substantially simultaneous manner.
U.S. Pat. No. 5,428,111 discloses a process for the living polymerization of aromatic, preferably styrenic monomers initiated from a living polyolefin, particularly polyisobutylene, chain end for making block copolymers having polyolefin mid-blocks and styrenic end-blocks.
U.S. Pat. No. 5,448,000 discloses a one-pot method of preparing sulfonic acid-terminated polyisobutylene by sulfonation with acetyl sulfate of a living polyisobutylene in a single step. The method involves “inifer” initiated carbocationic polymerization with Lewis acid to form the polymer followed by the sulfonation.
U.S. Pat. Nos. 5,637,647 and 5,677,386 disclose the capping of a living polymer with one or more capping compounds comprising non-polymerizable monomer selected from a group consisting of substituted or unsubstituted diphenyl alkylene, methoxystyrene, trans-stilbene, 1-isopropenylnaphthalene and 2,4-dimethyl styrene.
U.S. patent application Ser. No. 10/433,439, Publication No. 2004/0015029 A1, discloses a process for the preparation of polyisobutylenes in which, at least 60 percent of the polymer chains have at least one olefinically unsaturated terminal group, by cationic polymerization of isobutylene or isobutylene-containing monomer mixtures in the condensed phase and in the presence of an initiator system.
U.S. patent application Ser. No. 10/600,898, Publication No. 2004/0260033 A1, discloses the method for manufacturing and producing monodisperse telechelic polymers through cationic polymerization of suitable monomer under living polymerization conditions and quenching the polymerization with an N-substituted-pyrrole. The functionalized polymers containing N-substituted-pyrroles may be employed as fuel additives and/or lubricating oil additives.
PCT International Application No. PCT/EP/05472, International Publication No. WO99/09074, discloses a process for functionalizing polymers prepared by cationic polymerization wherein a living carbocationic polymerization system is reacted with one or more aromatic ring systems, and the use of substituted or unsubstituted reaction products of said process in lubricating oil or fuel compositions and additive concentrates, for example as dispersants, detergents or antioxidant additives or VI improvers.
β-Proton elimination by Free Bases in the Living cationic Polymerization of Isobutylene, by Young Cheol Bae and Rudolf Faust, Macromolecules, Volume 30, 7341-7344 (1997). The authors investigated β-proton elimination from quasi-living polyisobutylene, after observing exo-olefin formation in the presence of 2,6-di-tert-butylpyridine (DTBP) of low purity. They ascribed elimination to the presence of a sterically hindered cyclic imine base present in the DTBP in a concentration of 6×10−6 moles per liter. They simulated this impurity using 2-tert-butylpyridine (TBP) and discovered that the latter, when added to the reactor at the start of the polymerization (i.e., in the presence of monomer) resulted in about 65 percent elimination after 3 hours of reaction time to produce exclusively exo-olefin. When the extent of elimination had reached 20 percent or higher, significant coupling was observed from both 1H NMR and GPC analyses. Bae and Faust clearly considered that elimination by sterically hindered bases such as TBP was undesirable and should be avoided. The first paragraph of the paper was summarized as follows: “Finally, strong bases may also eliminate β-protons, which should be avoided.” Later, they refer to the cyclic imine base impurity in DTBP as “the culprit”. Finally, they summarized the entire paper by saying that the elimination process should be avoided for polymer preparation purposes, although it might facilitate the measurement of kinetic rate constants: “While β-proton elimination should be avoided for the synthesis of well-defined macromolecules, if diffusion control of this process can be shown, it may provide a novel method of establishing the concentration of active centers, from which absolute propagation rate constants could be calculated.”
SUMMARY OF THE INVENTION
The present invention is directed to a method for the preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring. The method also involves use of Lewis acid and an electron donor, or a common ion salt or its precursor to form the cationic quasi-living polyolefin polymer to which is added the quenching agent to form the polymer product.
More specifically, the present invention is directed to a method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles having at least two hydrocarbyl substituents attached to the aromatic ring, provided the nitrogen containing five-membered aromatic ring is not:
•(a) 2,4-dimethylpyrrote;
•(b) 1,2,5-trimethylpyrrole;
•(c) 2-phenylindole;
•(d) 2-methylbenzimidazole;
•(e) 1,2-dimethylimidazole;
•(f) 2-phenylimidazole; and
•(g) 2,4,5-triphenylimidazole.
Preferably the quenching is carried out at a temperature in the range of from about −130° C. to about 10° C. More preferably the quenching is carried out at a temperature from about −80° C. to about 0° C., and even more preferably from about −72° C. to about −10° C. Most preferably the quenching is carried out at a temperature in the range of from about −60° C. to about −20° C.
Preferably the polyolefin is polyisobutylene.
In a preferred embodiment of the present invention the polyolefin is prepared in situ.
The nitrogen-containing five-membered aromatic ring employed in an embodiment of the present invention is a substituted pyrrole.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0150539.html
Method For Preparation Of Polyolefins Containing Exo-Olefin Chain Ends (The University Of Southern Mississippi; and Chevron Oronite Company Llc)
United States Patent Application 20130150539
Inventors:
Stokes, Casey D. (Belle Chasse, LA, US)
Storey, Robson F. (Hattiesburg, MS, US)
Harrison, James J. (Novato, CA, US)
Application Number:
13/765563
Publication Date:
06/13/2013
Assignee:
The University Of Southern Mississippi (Hattiesburg, Ms, Us)
Chevron Oronite Company Llc (San Ramon, Ca, Us)
Abstract:
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with a nitrogen-containing five-membered aromatic ring having at least two hydrocarbyl substituent compounds attached to the ring.
FIELD OF THE INVENTION
The present invention is directed to a method for preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring.
BACKGROUND OF THE INVENTION
Linear polyolefins made using a mono-functional initiator containing a single “exo-olefin”, “1,1-di-substituted” olefin, or “methylvinylidene,” end group are useful precursors for the preparation of polymers containing specific functional end groups. Polymers made using multi-functional initiators would have multiple exo-olefinic end groups. Polymers containing specific end groups are useful as lubricating oil additives. One example of a functionalized polymer containing hetero atoms is polyisobutenylsuccinic anhydride. Functional end groups may also be desirable for making polymers with potential for further reactions.
Conventional ionic polymerizations can be anionic or cationic. Anionic polymerizations proceed, in the presence of a base, through carbanions and favor monomers having electron withdrawing groups. Cationic polymerizations proceed, in the presence of an acid, through a carbocation, also called a carbenium ion, and favor monomers that have electron releasing groups.
Similarly to the conventional polymerization systems, living polymerization systems may be either anionic or cationic. The difference between conventional polymerizations and living polymerizations is that an ideal living polymerization proceeds in the absence of chain transfer and chain termination. Living polymerization systems are of great commercial importance because the degree of polymerization may be controlled by controlling the feed ratio of monomer to initiator and sequential addition of two or more different monomers affords the ability to produce block copolymers. Polymerization continues until the monomer is exhausted, but the polymers retain their ability to add additional monomers any time in the future. A number of such systems are well known in the art.
A further development is the cationic quasi-living polymerization systems using conventional monomers. Quasi-living polymerization requires certain restrictive conditions, for example anhydrous reagents. Cationic quasi-living polymerizations differ from truly living polymerizations in that, although the rate of chain transfer approaches zero, chain termination is present but reversible. One important example of a cationic quasi-living polymerization is the cationic quasi-living polymerization of isobutylene.
Typically, cationic quasi-living polymerizations of isobutylene yield narrow molecular weight distribution and one major polymer product containing the 2-chloro-2-methylpropyl end group, also referred to as the “tert-chloride” end group. Under certain conditions minor amounts of olefinic isomers may also be produced.
On the other hand, there are two major olefinic isomers produced during conventional polymerization of isobutylene with BF3, for example, the highly reactive exo-olefin isomer and the relatively unreactive 2-methyl-1-propenyl isomer, also referred to as the “tri-substituted” isomer or “endo olefin” isomer. Furthermore, conventional polymerizations of isobutylene yield polymers with broad molecular weight distributions or polydispersity indices.
Exclusive production of the exo-olefin isomer has not been previously achieved under conventional polymerization conditions.
There are two established methods for producing polyisobutylene containing only the exo-olefin end group. One method involves chemical dehydrohalogenation of tert-chloride terminated polyisobutylene using potassium tert-butoxide in a post polymerization reaction (U.S. Pat. No. 4,342,849). The other method involves in situ quenching of quasi-living isobutylene with methallyltrimethylsilane, which converts an active, living carbenium ion to the exo-olefin end group. (M. Roth and H. Mayr, Macromolecules, 29, 6104, 1996)
Polyisobutylene polymers containing more than one exo-olefin end group may be prepared using the above methods by the use of a multi-functional initiator.
The preparation of polyolefins, including polyisobutylene polymers, is well known in the art. A number of patents have discussed processes for making polyisobutylene polymers containing exo-olefin end groups, but none using quenching a cationic quasi-living polymerization system with one or more nitrogen-containing five-membered aromatic ring compounds.
European Patent No. 341012 discloses a method for producing polymers with narrow molecular weight distribution, where the ratio of the weight average molecular weight, M(w), to the number average molecular weight, M(n), approaches 1.
U.S. Pat. No. 4,152,499 discloses isobutylene polymers having a mean degree of polymerization from 10 to 100 and where the proportion of theoretically possible terminal double bonds is greater than in products prepared using aluminum trichloride. The patent also discloses the method of making the isobutylene polymers using boron trifluoride as the initiator.
U.S. Pat. No. 4,342,849 discloses the synthesis of polyisobutylene carrying either unsaturation or hydroxyl groups at both ends, in the case of a linear polymer, or at all ends in the case of a star polymer. The method involves the steps of refluxing a solution of telechelic di-halogen polyisobutylene, adding a solution strong base such as potassium t-butoxide and stirring to form the telechelic di-olefin polyisobutylene.
U.S. Pat. No. 4,393,199 discloses a method for carrying out cationic polymerization with molecular weight control in which a pre-initiator and a catalyst effective for cationic polymerization are mixed with a monomer. The resulting living polymer is then treated as desired.
U.S. Pat. No. 4,758,631 discloses a method of preparing allyl-terminated polyisobutylene by allylation with allyltrimethylsilane of tertiary chloro-capped polyisobutylene by electrophilic substitution. The synthesis begins with the boron trichloride catalyzed mono- or oligo-tertiary chloride “inifer” initiated polymerization of isobutylene, followed in the same reaction vessel by the addition of hexane, allyltrimethylsilane and titanium tetrachloride.
U.S. Pat. Nos. 4,910,321 and 5,122,572 disclose a catalyst composed of a complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. Nos. 4,929,683 and 5,066,730 disclose a catalyst composed of a complex of an organic ether and a Lewis acid, preferably boron trichloride that can add olefin monomers to increase the molecular weight of the complex from as low as 200 to in excess of a million. The patents also disclose polymers of different molecular weights having useful end groups such as halogens and specifically chloride, allyl, acryl or methacryl, acetate or formate.
U.S. Pat. No. 5,219,948 discloses a method for preparing elastomeric polymers comprising alpha-olefins or conjugated alkadienes by cationic polymerization in the presence of titanium tetrachloride and an electron pair donor selected from pyridine or a non-hindered alkylpyridine. The polymers have very narrow, mono-modal molecular weight distribution.
U.S. Pat. No. 5,336,745 discloses a method for the direct synthesis of polymeric materials functionalized with desirable nitrogen-containing functional groups such as terminal azido, cyano, carbonylamino or thiocarbonylamino groups. Polymerization and functionalization occur in a substantially simultaneous manner.
U.S. Pat. No. 5,428,111 discloses a process for the living polymerization of aromatic, preferably styrenic monomers initiated from a living polyolefin, particularly polyisobutylene, chain end for making block copolymers having polyolefin mid-blocks and styrenic end-blocks.
U.S. Pat. No. 5,448,000 discloses a one-pot method of preparing sulfonic acid-terminated polyisobutylene by sulfonation with acetyl sulfate of a living polyisobutylene in a single step. The method involves “inifer” initiated carbocationic polymerization with Lewis acid to form the polymer followed by the sulfonation.
U.S. Pat. Nos. 5,637,647 and 5,677,386 disclose the capping of a living polymer with one or more capping compounds comprising non-polymerizable monomer selected from a group consisting of substituted or unsubstituted diphenyl alkylene, methoxystyrene, trans-stilbene, 1-isopropenylnaphthalene and 2,4-dimethyl styrene.
U.S. patent application Ser. No. 10/433,439, Publication No. 2004/0015029 A1, discloses a process for the preparation of polyisobutylenes in which, at least 60 percent of the polymer chains have at least one olefinically unsaturated terminal group, by cationic polymerization of isobutylene or isobutylene-containing monomer mixtures in the condensed phase and in the presence of an initiator system.
U.S. patent application Ser. No. 10/600,898, Publication No. 2004/0260033 A1, discloses the method for manufacturing and producing monodisperse telechelic polymers through cationic polymerization of suitable monomer under living polymerization conditions and quenching the polymerization with an N-substituted-pyrrole. The functionalized polymers containing N-substituted-pyrroles may be employed as fuel additives and/or lubricating oil additives.
PCT International Application No. PCT/EP/05472, International Publication No. WO99/09074, discloses a process for functionalizing polymers prepared by cationic polymerization wherein a living carbocationic polymerization system is reacted with one or more aromatic ring systems, and the use of substituted or unsubstituted reaction products of said process in lubricating oil or fuel compositions and additive concentrates, for example as dispersants, detergents or antioxidant additives or VI improvers.
β-Proton elimination by Free Bases in the Living cationic Polymerization of Isobutylene, by Young Cheol Bae and Rudolf Faust, Macromolecules, Volume 30, 7341-7344 (1997). The authors investigated β-proton elimination from quasi-living polyisobutylene, after observing exo-olefin formation in the presence of 2,6-di-tert-butylpyridine (DTBP) of low purity. They ascribed elimination to the presence of a sterically hindered cyclic imine base present in the DTBP in a concentration of 6×10−6 moles per liter. They simulated this impurity using 2-tert-butylpyridine (TBP) and discovered that the latter, when added to the reactor at the start of the polymerization (i.e., in the presence of monomer) resulted in about 65 percent elimination after 3 hours of reaction time to produce exclusively exo-olefin. When the extent of elimination had reached 20 percent or higher, significant coupling was observed from both 1H NMR and GPC analyses. Bae and Faust clearly considered that elimination by sterically hindered bases such as TBP was undesirable and should be avoided. The first paragraph of the paper was summarized as follows: “Finally, strong bases may also eliminate β-protons, which should be avoided.” Later, they refer to the cyclic imine base impurity in DTBP as “the culprit”. Finally, they summarized the entire paper by saying that the elimination process should be avoided for polymer preparation purposes, although it might facilitate the measurement of kinetic rate constants: “While β-proton elimination should be avoided for the synthesis of well-defined macromolecules, if diffusion control of this process can be shown, it may provide a novel method of establishing the concentration of active centers, from which absolute propagation rate constants could be calculated.”
SUMMARY OF THE INVENTION
The present invention is directed to a method for the preparation of polyolefins containing exo-olefin chain ends. The method involves quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds having at least two hydrocarbyl substituents attached to the ring. The method also involves use of Lewis acid and an electron donor, or a common ion salt or its precursor to form the cationic quasi-living polyolefin polymer to which is added the quenching agent to form the polymer product.
More specifically, the present invention is directed to a method for preparing a polyolefin containing one or more exo-olefinic end groups on the polymer chain, comprising quenching a cationic quasi-living polyolefin polymer system with one or more nitrogen-containing five-membered aromatic ring compounds selected from pyrroles and imidazoles having at least two hydrocarbyl substituents attached to the aromatic ring, provided the nitrogen containing five-membered aromatic ring is not:
•(a) 2,4-dimethylpyrrote;
•(b) 1,2,5-trimethylpyrrole;
•(c) 2-phenylindole;
•(d) 2-methylbenzimidazole;
•(e) 1,2-dimethylimidazole;
•(f) 2-phenylimidazole; and
•(g) 2,4,5-triphenylimidazole.
Preferably the quenching is carried out at a temperature in the range of from about −130° C. to about 10° C. More preferably the quenching is carried out at a temperature from about −80° C. to about 0° C., and even more preferably from about −72° C. to about −10° C. Most preferably the quenching is carried out at a temperature in the range of from about −60° C. to about −20° C.
Preferably the polyolefin is polyisobutylene.
In a preferred embodiment of the present invention the polyolefin is prepared in situ.
The nitrogen-containing five-membered aromatic ring employed in an embodiment of the present invention is a substituted pyrrole.
Free Full Text Source: http://www.freepatentsonline.com/y2013/0150539.html
Methods of Mercaptanizing Olefinic Hydrocarbons and Compositions Produced Therefrom (Chevron Phillips Chemical Company Lp)
PATENT
Methods of Mercaptanizing Olefinic Hydrocarbons and Compositions Produced Therefrom (Chevron Phillips Chemical Company Lp)
Publication number
US20130240780 A1
Application number
US 13/891,224
Publication date
Sep 19, 2013
Inventors
Michael S. Matson, 5 More »
Original Assignee
Chevron Phillips Chemical Company Lp
Abstract
The present invention discloses processes for forming polythiol compositions from olefinic hydrocarbons such as cyclooctadiene, cyclododecatriene, and trivinylcyclohexane. The polythiol compositions produced from these processes, including the sulfur-containing compounds of these compositions, also are described.
BACKGROUND OF THE INVENTION
The present invention relates generally to processes for producing polythiol compositions, and the compositions produced from these processes.
Polythiol compositions disclosed herein can be used as curing agents in adhesive and other applications.
SUMMARY OF THE INVENTION
Processes for forming polythiol compositions are disclosed herein. In accordance with embodiments of the present invention, one such process comprises:
1) contacting
• ◦a) a hydrocarbon compound having at east two olefinic double bonds;
◦b) H2S; and
◦c) a phosphite compound; and
2) forming the polythiol composition.
In this process, the molar ratio of H2S to olefinic double bond of the hydrocarbon compound can be in a range from 10:1 to 500:1.
Embodiments of this invention also are directed to polythiol compositions comprising sulfur-containing compounds produced by the disclosed processes.
Further, polythiol compositions derived from hydrocarbon compounds having at least two olefinic double bonds—for instance, compounds such as cyclooctadiene, cyclododecatriene, and trivinylcyclohexane—are disclosed. These polythiol compositions comprise sulfur-containing compounds, and the specific sulfur-containing compounds and their relative presence within the respective polythiol compositions are described.
Free Full Text Source: http://www.google.com/patents/US20130240780
Methods of Mercaptanizing Olefinic Hydrocarbons and Compositions Produced Therefrom (Chevron Phillips Chemical Company Lp)
Publication number
US20130240780 A1
Application number
US 13/891,224
Publication date
Sep 19, 2013
Inventors
Michael S. Matson, 5 More »
Original Assignee
Chevron Phillips Chemical Company Lp
Abstract
The present invention discloses processes for forming polythiol compositions from olefinic hydrocarbons such as cyclooctadiene, cyclododecatriene, and trivinylcyclohexane. The polythiol compositions produced from these processes, including the sulfur-containing compounds of these compositions, also are described.
BACKGROUND OF THE INVENTION
The present invention relates generally to processes for producing polythiol compositions, and the compositions produced from these processes.
Polythiol compositions disclosed herein can be used as curing agents in adhesive and other applications.
SUMMARY OF THE INVENTION
Processes for forming polythiol compositions are disclosed herein. In accordance with embodiments of the present invention, one such process comprises:
1) contacting
• ◦a) a hydrocarbon compound having at east two olefinic double bonds;
◦b) H2S; and
◦c) a phosphite compound; and
2) forming the polythiol composition.
In this process, the molar ratio of H2S to olefinic double bond of the hydrocarbon compound can be in a range from 10:1 to 500:1.
Embodiments of this invention also are directed to polythiol compositions comprising sulfur-containing compounds produced by the disclosed processes.
Further, polythiol compositions derived from hydrocarbon compounds having at least two olefinic double bonds—for instance, compounds such as cyclooctadiene, cyclododecatriene, and trivinylcyclohexane—are disclosed. These polythiol compositions comprise sulfur-containing compounds, and the specific sulfur-containing compounds and their relative presence within the respective polythiol compositions are described.
Free Full Text Source: http://www.google.com/patents/US20130240780
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