U.S. patent application number 16/286093 was filed with the patent office on 2019-06-20 for renewable source-derived polymer oil macroinitiators and thermoplastic block copolymers derived therefrom.
The applicant listed for this patent is Archer Daniels Midland Company. Invention is credited to Paul Bloom, Erik Hagberg.
Application Number | 20190185607 16/286093 |
Document ID | / |
Family ID | 56614776 |
Filed Date | 2019-06-20 |
![](/patent/app/20190185607/US20190185607A1-20190620-C00001.png)
United States Patent
Application |
20190185607 |
Kind Code |
A1 |
Bloom; Paul ; et
al. |
June 20, 2019 |
RENEWABLE SOURCE-DERIVED POLYMER OIL MACROINITIATORS AND
THERMOPLASTIC BLOCK COPOLYMERS DERIVED THEREFROM
Abstract
Compositions comprising renewable source derived polymer oil
polymerization macroinitiators and multiblock polymer compositions
derived therefrom by atom transfer radical polymerization are
disclosed. Hard, glossy multiblock copolymers, thermoset multiblock
copolymers, thermoplastic block copolymer elastomers, and methods
of making and using these types of materials are disclosed.
Inventors: |
Bloom; Paul; (Forsyth,
IL) ; Hagberg; Erik; (Decatur, IL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Archer Daniels Midland Company |
Decatur |
IL |
US |
|
|
Family ID: |
56614776 |
Appl. No.: |
16/286093 |
Filed: |
February 26, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15548844 |
Aug 4, 2017 |
10253132 |
|
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PCT/US16/17077 |
Feb 9, 2016 |
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16286093 |
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62113651 |
Feb 9, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2555/84 20130101;
C08L 2555/82 20130101; C08F 293/005 20130101; C08L 2555/32
20130101; C08F 242/00 20130101; C11C 3/00 20130101; C09F 7/00
20130101; C08F 2438/01 20130101; C08L 95/00 20130101 |
International
Class: |
C08F 293/00 20060101
C08F293/00; C08L 95/00 20060101 C08L095/00; C09F 7/00 20060101
C09F007/00; C08F 242/00 20060101 C08F242/00; C11C 3/00 20060101
C11C003/00 |
Claims
1. A polymer made using a polymerization macroinitiator comprised
of at least one halogenated polymer oil selected from the group
consisting of halogenated heat-bodied oil, a halogenated blown oil,
a halogenated copolymer oil, a halogenated hydrogenated heat-bodied
oil, a halogenated hydrogenated blown oil, a halogenated
hydrogenated copolymer oil, and combinations of any thereof, and
further wherein the polymerization macroinitiator comprises at
least one halogenated polymer oil obtained from a renewable
source-derived oil or fat.
2. The polymer of claim 1, made using a polymerization
macroinitiator including at least one halogenated polymer oil
obtained from a renewable source derived fat or oil selected from
the group consisting of algal oil, animal fat, beef tallow, borneo
tallow, butterfat, camelina oil, candlefish oil, canola oil, castor
oil, cocoa butter, cocoa butter substitutes, coconut oil, cod-liver
oil, colza oil, coriander oil, corn oil, cottonseed oil, false flax
oil, flaxseed oil, float grease from wastewater treatment
facilities, hazelnut oil, hempseed oil, herring oil, illipe fat,
jatropha oil, kokum butter, lanolin, lard, linseed oil, mango
kernel oil, marine oils, meadowfoam oil, menhaden oil, microbial
oil, milk fat, mowrah fat, mustard oil, mutton tallow, neat's foot
oil, oiticica oil, olive oil, orange roughy oil, palm oil, palm
kernel oil, palm kernel olein, palm kernel stearin, palm olein,
palm stearin, peanut oil, phulwara butter, pile herd oil, plant
oil, pork lard, radish oil, ramtil oil, rapeseed oil, rice bran
oil, safflower oil, sal fat, salicornia oil, sardine oil, sasanqua
oil, sesame oil, shea fat, shea butter, single-cell oil, soybean
oil, sunflower seed oil, tall oil, tallow, tigernut oil, tsubaki
oil, tung oil, triacylglycerols, triolein, used cooking oil,
vegetable oil, walnut oil, whale oil, white grease, yellow grease,
and derivatives, conjugated derivatives, genetically-modified
derivatives, and combinations of any thereof.
3. The polymer of claim 1, made using a polymerization
macroinitiator including at least one halogenated polymer oil
obtained from a renewable source derived fat or oil containing one
or more conjugated fatty acids selected from the group consisting
of conjugated linoleic acids, rumenic acid (9-cis,
11-trans-octadecadienoic acid), 10-trans, 12-trans-octadecadienoic
acid, 10-trans, 12-cis-octadecadienoic acid, conjugated linolenic
acid, alpha-eleostearic acid (9-cis, 11-trans, 13-trans
octadecatrienoic acid), beta-eleostearic acid (9-trans, 11-trans,
13-trans octadecatrienoic acid), rumelenic acid
(9-cis,11-trans,15-cis-octadecatrienoic acid), punicic acid
(9-cis,11-trans,13-cis-octadecatrienoic acid), catalpic acid
(9-trans, 11-trans, 13-cis-octadecatrienoic acid), alpha-calendic
acid (8-trans, 10-trans, 12-cis octadecatrienoic acid),
beta-calendic acid (8-trans, 10-trans, 12-trans octadecatrienoic
acid), jacaric acid (8-cis, 10-trans, 12-cis octadecatrienoic
acid), tetraenoic acids, alpha-parinaric acid
(9-trans,11-cis,13-cis, 15-trans-octadecatetraenoic acid),
beta-parinaric acid (9-trans,11-trans,13-trans,
15-trans-octadecatetraenoic acid), 2-trans, 4-trans, 6-trans,
11-cis octadecatetraenoic acid from rhibozium bacteria, pentaenoic
acids, bosseopentaenoic acid (5-cis, 8-cis, 10-trans, 12-trans, 14
cis-pentaenoic acid), hexaenoic acid, 4-cis, 7-cis, 9-trans,
13-cis, 16-cis, 19-cis docosahexaenoic acid from marine algae, and
combinations of any thereof.
4. A polymer composition including the polymer of claim 1 and a
polymer selected from the group consisting of acrylonitrile
butadiene styrene, polyvinyl halide products, nylons, polyesters,
polypropylene alloys, chlorinated polyethylenes, polycarbonates,
polystyrenes, acrylics, and combinations of any thereof.
5. The polymer of claim 1, wherein the polymer is a thermoplastic
elastomer including at least one A block made from monomers
selected from the group consisting of styrene, alpha-methyl
styrene, t-butyl styrene, vinyl, vinyl xylene, vinyl naphthalene,
vinyl pyridine, divinyl benzene, methyl acrylate, C.sub.1-C.sub.6
(meth)acrylate, methyl methacrylate, ethyl methacrylate, propyl
(meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl
(meth)acrylate), acrylonitrile, adiponitrile, methacrylonitrile,
butadiene, isoprene, a vinyl aromatic monomer, a polystyrene
homopolymer, a diolefin, a nitrile, a dinitrile, and combinations
of any thereof.
6. An asphalt composition comprising the polymer of claim 1 and
asphalt.
7. The asphalt composition of claim 6, further comprising an
antioxidant.
Description
CLAIM OF PRIORITY
[0001] The present Application is a divisional application of U.S.
patent application Ser. No. 15/548,844, filed Aug. 4, 2017, which
is a national stage entry of International Application No.
PCT/US2016/017077, filed 11 Feb. 9, 2016, which claims benefit of
U.S. Provisional Patent Application No. 62/113,651, filed on Feb.
9, 2015, the contents of each are herein incorporated by this
reference.
TECHNICAL FIELD
[0002] The present invention relates to renewable source derived
polymer oil polymerization macroinitiators and to thermoplastic
multiblock copolymer compositions derived therefrom, and more
particularly to hard, glossy multiblock copolymers, thermoset
multiblock copolymers, thermoplastic block copolymer elastomers,
and to methods of making and using these types of materials.
BACKGROUND OF THE INVENTION
[0003] Polymers from vegetable oils have obtained increasing
attention as public policy makers and corporations alike have been
interested in replacing traditional petrochemical feedstocks due to
their environmental and economic impact. In recent years, the cost
of renewable source derived monomers has become highly competitive
(and in many cases more economical than petrochemical feedstocks).
For example, with appropriate modification of soybean oil (such as
conjugation of triglycerides, or development of soybean oil types
that are particularly suitable for polymerization), the chemical
properties, thermal properties, microstructure and morphology, and
mechanical/rheological behaviors of soybean oil-based polymers
could be fine-tuned to make these biopolymers highly useful in the
plastics industry.
[0004] To date, some success has been achieved through the
application of traditional cationic and free radical polymerization
routes to vegetable oils to yield thermoset plastics. Pfister &
Larock, Bioresource Technology 101:6200(2010), which is hereby
incorporated by reference in its entirety, have researched a
variety of polymers, ranging from soft rubbers to hard, tough
plastics using cationic copolymerization of vegetable oils, mainly
SBO, to produce thermoset plastics with boron triflouride
diethyletherate (BFE) as the initiator. Lu et al. synthesized
soybean-oil-based waterborne polyurethane films with different
properties ranging from elastomeric polymers to rigid plastics by
changing the polyol functionality and hard segment content of the
polymers (Lu et al., Polymer 46:71 (2005); Lu et al., Progress in
Organic Coatings 71:336 (2011), which are hereby incorporated by
reference in their entirety). Bunker et al. have reported the use
of soybean oil to synthesize different bio-based products such as
sheet molding composites, elastomers, coatings, foams, etc. For
instance, Bunker et al. were able to synthesize pressure-sensitive
adhesives using mini-emulsion polymerization of acrylated methyl
oleate, a monoglyceride derived from soy bean oil (Bunker et al,
International Journal of Adhesion and Adhesives 23:29 (2003);
Bunker & Wool, Journal of Polymer Science Part A: Polymer
Chemistry 40:451 (2002), which are hereby incorporated by reference
in their entirety). The polymers produced were comparable to their
petroleum counterparts.
[0005] Zhu et al. were able to generate an elastic network based on
acrylated oleic methyl ester through bulk polymerization using
ethylene glycol as the crosslinker (Zhu & Wool, Polymer 47:8106
(2006), which is hereby incorporated by reference in its entirety).
Lu et al. were also able to create thermosetting resins synthesized
from soybean oil that can be used in sheet molding compound
applications. These resins were synthesized by introducing acid
functionality and onto the soybean. The acid groups reacted with
divalent metallic oxides or hydroxides forming the sheet, while the
carbon-carbon groups are subject to free radical polymerization (Lu
et al., Polymer 46:71 (2005), which is hereby incorporated by
reference in its entirety). Bonnaillie et al. were able to create a
thermoset foam system using a pressurized carbon dioxide foaming
process of acrylated epoxidized soybean oil (AESO) (Bonnaillie
& Wool, Journal of Applied Polymer Science 105:1042 (2007),
which is hereby incorporated by reference in its entirety). Wool et
al. were able to synthesize liquid molding resins that were able to
be cured into high modulus thermosetting polymers and composites
using triglycerides derived from plant oils (U.S. Pat. No.
6,121,398 to Wool et al., which is hereby incorporated by reference
in its entirety).
[0006] Block copolymers may be thermosetting or thermoplastic with
broad areas of application including as rubbers or elastomers; as
toughened engineering thermoplastics; as asphalt modifiers; as
resin modifiers; as engineering resins; as leather and cement
modifiers; in footwear, such as in rubber shoe heels, rubber shoe
soles; in automobiles, such as in tires, hoses, power belts,
conveyor belts, printing rolls, rubber wringers, automobile floor
mats, mud flaps for trucks, ball mill liners, and weather strips;
as adhesives, such as pressure sensitive adhesives; in aerospace
equipment; as viscosity index improvers; as detergents; as
diagnostic agents and supports therefore; as dispersants; as
emulsifiers; as lubricants and/or surfactants; as paper additives
and coating agents; and in packaging, such as food and beverage
packaging materials.
[0007] Styrenic block copolymers (SBCs), such as styrene-butadiene
type polymers (e.g., styrene-butadiene di-block, SB;
styrene-butadiene-styrene tri-block, SBS) of the type sold by
Kraton Performance Polymers, Inc. under the Kraton.RTM. mark, have
historically served the asphalt and footwear industries for years,
with markets also in the industries of packaging, pressure
sensitive adhesives, packaging materials, pressure sensitive
adhesives, tires, packaging materials, footwear, and as a modifier
of bitumen/asphalt, which is one of its largest markets.
[0008] With the forecast of increasing demand of liquid asphalt for
the next decade, a particularly strong need exists for a new type
of cost effective, environmentally friendly, viable polymer that
can be used as an asphalt modifier in lieu of standard
styrene-butadiene type modifiers. The global asphalt market is
predicted to reach 118.4 million metric tons by 2015, according to
a January 2011 report by Global Industry Analysts, Inc. The asphalt
paving industry accounts for the largest end-use market segment of
asphalt. With increasing growth in the developing markets of China,
India, and Eastern Europe, asphalt will be increasingly needed to
construct roadway infrastructure for the next decade. The increased
demand for asphalt, along with the need for improved asphalt
materials/pavement performance, creates the opportunity for an
asphalt modifier.
[0009] In this regard, as background, the grade of the asphalt
governs the performance of paving mixtures at in-service
temperatures. In many cases, the characteristics of bitumen need to
be altered to improve its elastic recovery/ductility at low
temperatures for sufficient cracking resistance as well as to
increase its shearing resistance for sustained loads and/or at high
temperatures for rutting resistance. The physical properties of
bitumen are typically modified with the addition of SBS polymers to
produce an improved asphalt grade that enhances the performance of
asphalt paving mixtures. Of the asphalt mixtures that are polymer
modified, approximately 80% of polymer modified asphalt uses
SBS-type polymers.
[0010] Asphalt cement is commonly modified with poly
(styrene-block-butadiene-block-styrene) (SBS), a thermoplastic
elastomer (TPE). Polymer modification is known to substantially
improve the physical and mechanical properties of asphalt paving
mixtures. Polymer modification increases asphalt elasticity at high
temperatures, as a result of an increased storage modulus and a
decreased phase angle, which improves rutting resistance. It also
increases the complex modulus, but lowers creep stiffness at low
temperatures, thus improving cracking resistance (Isacsson &
Lu, "Characterization of Bitumens Modified With SEBS, EVA and EBA
Polymer," Journal of Materials Science 4:737-745 (1999), which is
hereby incorporated by reference in its entirety). SBS-type
polymers are typically added to asphalt pavements when additional
performance is desired or when optimizing life-cycle costs is
warranted. SBS allows for the production of many specialty mixes
including cold mixes, emulsion chip seals, and micro-surface
mixes.
[0011] SBSTPEs are block copolymers (BCPs) comprised of
styrene-butadiene-styrene polymer chains that create an ordered
morphology of cylindrical glassy polystyrene block domains within a
rubbery polybutadiene matrix (Bulatovic et al., "Polymer Modified
Bitumen," Materials Research Innovations 16(1):1-6(2012), which is
hereby incorporated by reference in its entirety). SBS polymers are
thermoplastic, meaning that they can be easily processed as liquids
at temperatures higher than their glass transition temperature due
to the linear nature of their chains. Upon cooling, the rigid
polystyrene end-blocks vitrify and act as anchors for the liquid
rubbery domains by providing a restoring force when stretched
(FRrEn J. R., Polymer Science and Technology (Prentice Hall, Upper
Saddle River, N.J., 2 ed. 2008), which is hereby incorporated by
reference in its entirety).
[0012] SBS is incorporated into asphalt through mixing and shearing
at high temperatures to uniformly disperse the polymer. When
blended with asphalt binder, the polymer swells within the asphalt
maltene phase to form a continuous tridimensional polymer network
(Lesueur, "The Colloidal Structure of Bitumen: Consequences on the
Rheology and on the Mechanisms of Bitumen Modification," Advances
in Colloid and Interface Science 145:42-82 (2009), which is hereby
incorporated by reference in its entirety). At high temperatures,
the polymer network becomes fluid yet still provides a stiffening
effect that increases the modulus of the mixture. At low
temperatures, a crosslinked network within the asphalt redevelops
without adversely affecting the low temperature cracking
performance due to the elastic properties of the polybutadiene
(Airey G. D., "Styrene Butadiene Styrene Polymer Modification of
Road Bitumens," Journal of Materials Science 39:951-959 (2004),
which is hereby incorporated by reference in its entirety). The
resulting performance properties widen the working temperature
range of the binder-polymer system.
[0013] The butadiene monomer used in SBS is typically derived from
petrochemical feedstocks, a byproduct of ethylene production.
Unfortunately in light of the aforementioned growth in demand for
liquid asphalt, however, the price of butadiene has been rapidly
increasing not only due to increases in the price of crude oil, but
also due to global market shifts in supply and demand. As shale gas
supplies become more abundant, crackers are more commonly using
lighter petrochemical feeds such as ethane to produce ethylene and
its co-products. However, using lighter feeds lowers butadiene
production, thus tightening the supply (Foster, "Lighter Feeds in
US Steam Crackers Brings New Attitude Toward On-purpose Butadiene,
Propylene Prospects," Platts Special Report: Petrochemicals 1-6
(2011), which is hereby incorporated by reference in its
entirety).
[0014] As briefly summarized above, vegetable oils have been
considered as monomeric feedstocks for the plastics industry in
general for over 20 years. To date, moderate success has been
achieved through the application of traditional cationic and free
radical polymerization routes to vegetable oils to yield thermoset
plastics (i.e., plastics which, once synthesized, permanently
retain their shape and are not subject to further processing).
However, the vast majority of commodity polymers are highly
processable thermoplastic materials, and the body of work related
to the development of vegetable oil-based alternatives to
conventional monomers like butadiene is much more limited.
[0015] Recently published US 2013/0184383 A1 to Cochran et al.,
"Thermoplastic Elastomers Via Atom Transfer Radical Polymerization
of Plant Oil" (hereafter, the "'383 Cochran et al." or "Cochran et
al." application, hereby incorporated by reference in its entirety
together with any publications incorporated by reference in turn by
Cochran et al.), however, describes novel thermoplastic elastomer
compositions from vegetable oil monomers and methods of making and
using the same. In particular, thermoplastic block copolymers are
described in the '383 Cochran et al. application which comprise a
block of radically polymerizable monomer and a block of polymerized
plant oil containing one or more triglyceride monomers.
[0016] In Cochran et al., the block copolymers in question are
summarized as comprising at least one PA block and at least one PB
block. The PA block represents a polymer block comprising one or
more units of monomer A, and the PB block represents a polymer
block comprising one or more units of monomer B. Monomer A is
described as a vinyl, acrylic, diolefin, nitrile, dinitrile, or
acrylonitrile monomer, while Monomer B is a radically polymerizable
plant oil monomer containing one or more triglycerides. The
vegetable oil triglycerides are discrete monomers comprising three
fatty acid chains esterified to a glycerol backbone.
[0017] Cochran et al. as well contemplates a method of preparing a
thermoplastic block copolymer or polymer block wherein a radically
polymerizable plant oil monomer containing one or more triglyceride
monomers is initially provided. This plant oil monomer is then
radically polymerized, in the presence of an initiator added as a
separate component and a transition-metal catalyst system to form a
thermoplastic polymer. This thermoplastic polymer can itself be
used as a thermoplastic elastomer, or can be used as a
thermoplastic polymer block and further polymerized with other
monomers to form a polymerized plant oil-based thermoplastic block
copolymer.
[0018] The addition of styrene to polymerized triglycerides helps
improve the processability, aids in the control of the melt state
properties of polymers (glass transition temperature (Tg), elastic
moduli, etc.) (Woof, R. P. & Sun, X. S., Bio-based polymers and
composites (Academic Press, Burlington, Mass. 2005), which is
hereby incorporated by reference in its entirety), and can serve as
physical crosslinking sites below the glass transition temperature
(Tg) of the polystyrene (100.degree. C.). In a typical SBS
elastomer, the styrene composition is about 10-30 wt % such that
spherical or cylindrical styrene domains form in a matrix of
butadiene. When the temperature is below the glass transition
temperature of polystyrene (T=100.degree. C.), the polybutadiene
matrix is liquid but is bound between the vitreous polystyrene
spheres, which serve as physical crosslinks. When the temperature
is above the glass transition temperature of polystyrene, the
entire elastomer system is molten and may be processed easily.
Crosslinked poly(soybean oil) has been reported to have T values as
low as -56.degree. C. (Yang et al., Journal of Polymers and the
Environment 19:189 (2011), which is hereby incorporated by
reference in its entirety). Accordingly, polymerized soybean oil is
an excellent candidate to serve as the liquid component in
thermoplastic elastomers based on styrenic block copolymers, and
polymers based on radically polymerizable renewable source-derived
polymer oil macroinitiator containing one or more polymer oils
comprise a significant improvement due to their crosslinked
nature.
SUMMARY OF THE INVENTION
[0019] The present invention, in one aspect, concerns an
improvement on Cochran et al., wherein thermoplastic block
copolymers are provided which are prepared from radically
polymerizable monomers A in common with Cochran et al. but
macroinitiators comprising halogenated polymer oils from renewable
source-derived oils and fats are used for the polymer block PB and
obviate the need for an added separate initiator. In a further
point of differentiation from Cochran et al., polymer block PB of
the present invention comprises a multiblock architecture. The
resulting multiblock polymers made from the macroinitiator of the
present invention can provide thermosetting or thermoplastic
polymers with certain properties, such as Number Average Molecular
Weight, polydispersity index, and glass transition temperature that
typically are associated with petroleum-based or -derived polymers
as presently used in a wide variety of applications.
[0020] These polymer oil macroinitiators comprising halogenated
polymerized renewable source-derived oils and fats are positioned
to be used with atom transfer radical polymerization (ATRP) as
contemplated by Cochran et al., but in contrast to the use of
acrylated epoxidized vegetable oil triglyceride monomers described
in Cochran et al., offer a number of advantages in the context of
making renewable oil-based thermoplastic multiblock copolymers by
ATRP according to a process otherwise generally as described in
Cochran et al. In particular, acrylated epoxidized vegetable oil
triglyceride monomers suffer from certain limitations as monomers,
such as higher viscosities, and the processes employed in making
polymers from acrylated epoxidized vegetable oil triglyceride
monomers suffer from limitations such as the need for several
steps, including hazardous and exothermic epoxidation.
[0021] However, these limitations are overcome in the present
invention by the use of macroinitiators comprising renewable
source-derived polymer oils. The polymer oils and fats used to
synthesize the macroinitiators comprise at least one of heat-bodied
oils, blown oils, and copolymer oils, collectively called "polymer
oils" herein, and are characterized by molecular crosslinks
occurring in the processes of making the blown oils, heat-bodied
oils, copolymer oils, or hydrogenated derivatives of these. The
polymer oils may be hydrogenated before or after making the blown
oils, heat-bodied oils, copolymer oils. Thus, in contrast to
acrylated epoxidized vegetable oil triglyceride monomers, the
polymer oil macroinitiators of the present invention are
crosslinked in the processes of making the blown oils, heat-bodied
oils, copolymer oils prior to polymerization with monomer A or
polymer block PA. As a result of the crosslinked structure of the
polymer oils used to make the macroinitiators, block copolymers
made from polymer oil macroinitiators can have high critical
entanglement molecular weights (at which the properties maximize in
respect to the viscosity of the molten polymer). The presence of
more than one macroinitiator site on a given polymer oil monomer
further enables the formation of multiblock copolymers with
desirable properties such as elasticity, toughness, tackiness, and
ease of melt-processing. What is meant by tackiness is the adhesive
characteristic; higher tackiness corresponds to a greater degree of
adhesiveness.
[0022] In another aspect, the present invention is concerned with
thermoplastic multiblock copolymer elastomers prepared from
radically polymerizable monomers and halogenated polymerized
renewable source-derived oils and fats. The halogenated polymerized
renewable source-derived oils and fats can be halogenated
heat-bodied oils, halogenated blown oils, halogenated copolymer
oils, or combinations of any thereof.
[0023] In another aspect, the present invention is concerned with
methods of using halogenated polymerized renewable source-derived
oil and/or fat-based thermoplastic polymers or block copolymers in
various applications wherein petroleum-based thermoplastic
polymers, block copolymers and block copolymer elastomers are
presently used, such as for asphalt modifiers, in adhesives, rubber
compositions, in the automobile industry, footwear, packaging,
etc.
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0024] Multiblock copolymers contemplated by the present invention
comprise at least one PA block and at least one PB block. The PA
block represents a polymer block comprising one or more units of
monomer A, and the PB block is a polymerized plant oil multiblock
comprising at least one of a heat-bodied oil, a blown oil, a
copolymer oil, a hydrogenated heat-bodied oil, a hydrogenated blown
oil, or a hydrogenated copolymer oil.
[0025] The heat-bodied oil, blown oil, copolymer oil, hydrogenated
heat-bodied oil, hydrogenated blown oil, or hydrogenated copolymer
oil (collectively referred to as "polymer oils") are halogenated to
form a halogenated heat-bodied oil, a halogenated blown oil, a
halogenated copolymer oil, a halogenated hydrogenated heat-bodied
oil, a halogenated hydrogenated blown oil, or a halogenated
hydrogenated copolymer oil, respectively (collectively referred to
as "halogenated polymer oils"). The halogenated polymer oil serves
as a macroinitiator and a B multiblock in subsequent Atom Transfer
Radical Polymerization, obviating the need to add a discrete
initiator molecule.
[0026] The multiblock copolymer can be a linear or branched
copolymer, and can contain two or more blocks. Exemplary copolymer
architectures includes, but are not limited to (PA-PB).sub.n,
(PA-PB).sub.n-PA, PB-(PA-PB).sub.n., and (Pa.sub.n'-PB).sub.n where
n and n' are greater than 0. For example, n ranges from 2 to 50, or
from 2 to 10 and n' ranges from 0.01 to 200.
[0027] The PA block is made by polymerizing one or more radically
polymerizable monomers, and has an average molecular weight of
about 1 to about 300 kDa, or about 10 to about 30 kDa. The PA block
may comprise repeating units of monomer A. For instance, the PA
block can be a polymerized linear-chain or branched-chain monomer A
or radicals thereof. The PB block is comprises one or more polymer
oil, and has an average molecular weight of about 2 kDa to about
500 kDa, or about 6 to about 100 kDa. The PB block may comprise
repeating units of polymer oil. For instance, the PB polymer oil
block can be a polymerized linear-chain or branched-chain polymer
oil or hydrogenated polymer oil, or radicals thereof.
[0028] PA-PB multiblock copolymers typically contain about 5 wt %
to about 95 wt % of the polymerized A block and about 95 wt % to
about 5 wt % of polymerized renewable source-derived polymer oil B
multiblock. What is meant by multiblock is a B component that may
have more than one site of polymerization initiation for addition
of a PA block, resulting in one or more PA blocks per PB block.
[0029] The PA block of the block copolymer can be considered as a
"hard" block, and has properties characteristic of thermoplastic
substances in that it has the stability necessary for processing at
elevated temperatures and yet possesses good strength below the
temperature at which it softens. The PA block is polymerized from
one or more radically polymerizable monomers, which can include a
variety type of monomers such as vinyl, acrylic, diolefin, nitrile,
dinitrile, or acrylonitrile monomer. Vinyl aromatic monomers are
exemplary vinyl monomers that can be used in the block copolymer,
and include any vinyl aromatics optionally having one or more
substituents on the aromatic moiety. The aromatic moiety can be
either mono- or polycyclic. Exemplary monomers for the PA block
include styrene, a-methyl styrene, t-butyl styrene, vinyl xylene,
vinyl naphthalene, vinyl pyridine, divinyl benzene, adiponitrile,
methacrylonitrile, butadiene, isoprene, and mixtures thereof.
Moreover, two or more different monomers can be used together in
the formation of the PA block. A typical radically polymerizable
monomer A used herein is styrene, and the resulting PA block is a
styrene homopolymer.
[0030] The PB block of the block copolymer can be considered as a
"soft" block, and has elastomeric properties which allow it to
absorb and dissipate an applied stress and then regain its shape.
The PB block comprises one or more renewable source-derived polymer
oils and fats containing one or more triglycerides. The renewable
source-derived polymer oils and fats used in the block copolymer
can be any plant oil that is radically polymerizable, in particular
those that contain one or more types of triglycerides, in
particular drying oils.
[0031] The processes of the present disclosure for making radically
polymerizable macroinitiators and for making block copolymers
therefrom begin with polymerized oils.
[0032] Linseed (flaxseed), rapeseed, safflower, soybean, tall,
oiticica, castor, marine organisms, single-cells, and algae are
examples of the sources of desirable triglyceride monomers used as
the starting materials for formation of polymerized oils. Any
renewable source derived fat or oil may be incorporated into the
triglyceride monomer starting materials, added to the polymer oils,
or added to the macroinitiators of the present invention. Drying
oils are preferred. Renewable source derived oil monomers comprise
derivatives of common oil triglycerides. What is meant by vegetable
oil monomer is a single triglyceride molecule. "Triglyceride," as
defined herein, may refer to any unmodified triglyceride naturally
existent in renewable source-derived oils and fats, including plant
oil, microbial oil, or animal fat as well as any derivatives of
unmodified triglycerides. An unmodified triglyceride may include
any ester derived from glycerol with three similar or different
fatty acids.
[0033] As previously mentioned, triglycerides are discrete monomers
comprising three fatty acid chains esterified to a glycerol
backbone. Typical commercially available renewable source derived
oil monomers include oils from linseed (flaxseed), rapeseed,
safflower, soybean, tall, oiticica, castor, marine organisms,
single-cells, and algae; these can be rich in double bonds. Other
renewable source derived oil monomers include animal fat, beef
tallow, borneo tallow, butterfat, camelina oil, candlefish oil,
canola oil, castor oil, cocoa butter, cocoa butter substitutes,
coconut oil, cod-liver oil, colza oil, coriander oil, corn oil,
cottonseed oil, false flax oil, flax oil, float grease from
wastewater treatment facilities, hazelnut oil, hempseed oil,
herring oil, illipe fat, jatropha oil, kokum butter, lanolin, lard,
linseed oil, mango kernel oil, marine oils, meadowfoam oil,
menhaden oil, milk fat, mowrah fat, mustard oil, mutton tallow,
neat's foot oil, olive oil, orange roughy oil, palm oil, palm
kernel oil, palm kernel olein, palm kernel stearin, palm olein,
palm stearin, peanut oil, phulwara butter, pork lard, radish oil,
ramtil oil, rapeseed oil, rice bran oil, safflower oil, sal fat,
salicornia oil, sardine oil, sasanqua oil, sesame oil, shea fat,
shea butter, soybean oil, sunflower seed oil, tall oil, tallow,
tigernut oil, tsubaki oil, tung oil, triacylglycerols, triolein,
used cooking oil, vegetable oil, walnut oil, whale oil, white
grease, yellow grease, and derivatives, conjugated derivatives,
genetically-modified derivatives, and mixtures of any thereof.
[0034] Conjugated triglycerides are defined as triglycerides
containing one or more conjugated fatty acids (fatty acids
containing at least one pair of conjugated double bonds). Exemplary
conjugated fatty acids are conjugated linoleic acids, such as
rumenic acid (9-cis, 11-trans-octadecadienoic acid); 10-trans,
12-trans-octadecadienoic acid; 10-trans, 12-cis-octadecadienoic
acid; conjugated linolenic acid, such as alpha-eleostearic acid
(9-cis, 11-trans, 13-trans octadecatrienoic acid); beta-eleostearic
acid (9-trans, 11-trans, 13-trans octadecatrienoic acid); rumelenic
acid (9-cis,11-trans,15-cis-octadecatrienoic acid); punicic acid
(9-cis,11-trans,13-cis-octadecatrienoic acid); catalpic acid
(9-trans, 11-trans, 13-cis-octadecatrienoic acid); alpha-calendic
acid (8-trans, 10-trans, 12-cis octadecatrienoic acid);
beta-calendic acid (8-trans, 10-trans, 12-trans octadecatrienoic
acid); jacaric acid (8-cis, 10-trans, 12-cis octadecatrienoic
acid); tetraenoic acids, such as alpha-parinaric acid
(9-trans,11-cis,13-cis, 15-trans-octadecatetraenoic acid);
beta-parinaric acid (9-trans,11-trans,13-trans,
15-trans-octadecatetraenoic acid); 2-trans, 4-trans, 6-trans,11-cis
octadecatetraenoic acid from rhibozium bacteria; pentaenoic acids,
such as bosseopentaenoic acid (5-cis, 8-cis, 10-trans, 12-trans, 14
cis-pentaenoic acid); hexapentaenoic acid, such as 4-cis, 7-cis,
9-trans, 13-cis, 16-cis, 19-cis docosahexaenoic acid from marine
algae. Triglyceride derivatives may include any triglyceride
monomers that contain conjugated systems (i.e., a system of
connected p-orbitals with delocalized electrons in triglycerides).
A conjugated triglyceride monomer may contain a single conjugated
site per triglyceride monomer. Alternatively, two or all three
fatty-acid chains of the triglyceride monomer may contain one or
more conjugated sites.
[0035] The multifunctional nature of highly unsaturated oils
(drying oils) allows crosslinking of triglyceride monomers, leading
to the formation of irreversibly crosslinked thermoset polymer
oils, such as heat-bodied oil, blown oil, or copolymer oil. Soybean
oil, for instance, is comprised of 86% of mono- and polyunsaturated
fatty acid molecules containing the required double bonds for
standard polymerization chemistry to produce polymerized oil
macromolecules.
[0036] Examples of polymer oils prepared from renewable
source-derived polyunsaturated oils include heat-polymerized
(heat-bodied) oil (also known as stand oil), blown oil, and
copolymer oil (Fox, F., Oils for Organic Coatings, in Federation
Series on Coatings Technology, Unit Three, Federation of Societies
for Paint Technology, Philadelphia, Pa., 1965, which is hereby
incorporated by reference in its entirety). These polymer oils are
widely available as products of commerce.
[0037] In the processes of converting triglyceride monomers into
the blown oils, heat-bodied oils, or copolymer oils, intermolecular
bonds are formed between renewable source derived triglyceride
monomers. The resulting products often have higher viscosity than
the starting triglyceride monomers and are inedible. In the
formation of polymer oils, triglycerides form dimers, trimers, and
oligomers, increasing entanglement (Paschke, R. F. and Wheeler, D.
H., Inter- and Intramolecular Polymerization in Heat-Bodied Linseed
Oil, J. Amer. Oil Chem. Soc. 31, pp. 208-211, 1954, which is hereby
incorporated by reference in its entirety). In addition,
intramolecular bonds are formed between fatty acids within
triglyceride monomers, increasing the crosslinking of polymer oils
with a resultant increase in critical entanglement molecular
weight.
[0038] In heat-bodying, depending on the oil used, triglyceride
monomers are heated and held at high temperature (an exemplary
range is between about 288.degree. C. to about 316.degree. C.) to
catalyze polymerization. Incubation with heat is continued until a
product with a desired viscosity is obtained. Longer reaction times
produce higher viscosity products due to increased levels of
crosslinking, often by formation of six-membered rings containing a
double bond; often the rings are intermolecular and join two
triglyceride monomer molecules into a dimer. (Heat bodying of
Drying Oils, J. Amer. Oil 27(11) 468-472, 1950). The viscosity of
heat bodied oils is described using a scale with values ranging
from P to Z.sub.9. During the heat-bodying (heat-polymerization)
reaction, the unsaturated triacylglycerols monomers react to form
polymers, such as dimers and trimers. As polymerization takes
place, the Iodine Value of the oil decreases due to the formation
of new carbon-carbon bonds between triacylglycerol units at sites
occupied by double bonds in the original triacylglycerols. Both
intermolecular and intramolecular bonds are formed. Ester bonds
between glycerol and fatty acids in the triglyceride monomers
remain largely intact. The significant changes undergone by linseed
oil as it is transformed by heat bodying from triglyceride monomers
to a polymer oil have been summarized ("Linseed oil. Changes in
physical and chemical properties during heat-bodying," Caldwell and
Mattiello, Ind. Eng. Chem. 24(2) 158-162 1932, which is hereby
incorporated by reference in its entirety). Heat bodied oils are
inedible and are used in coatings such as quick drying enamel,
oleoresin varnish, primers, lacquers, undercoats, flat paints,
mastics, sealants, jointing pastes, printing inks, wood
preservatives, rust inhibitor, and core oils. OKO M25.TM., OKO
M37.TM., Alinco Y.TM. and Alinco Z2/Z3.TM. are examples of
heat-bodied oils available from Archer Daniels Midland Company,
Decatur Ill., USA.
[0039] Another method for polymerizing triglyceride monomers is by
bubbling air through the oil while heating, usually with catalysts
(so-called "drier catalysts") such as metal soaps, fatty acids, or
salts of lead, manganese, and cobalt, to form "blown oils" with a
broad variety of industrial applications, The oil is polymerized
and partially oxidized and free hydroxyl groups are formed. For
example, blown oils are prepared by polymerization and partial
oxidation by bubbling air through a triglyceride monomer while
heating to temperatures of about 110.degree. C. (U.S. Pat. No.
7,842,746 to Bloom and Holzgraefe, issued Nov. 30, 2010:
"Hydrogenated and Partially Hydrogenated Heat-Bodied Oils and Uses
Thereof;" Fox, F., Federation Series on Coatings Technology, Unit
Three (1965) pages 25-26, which are hereby incorporated by
reference in their entirety). Blown triacylglycerol oils have
carbon-carbon and ether linkages between triacylglycerol units.
(Teng, G. et al., Surface Coatings International, Part B: Coatings
Transactions 86(B3): 221-229 (2003), Abstract, which is hereby
incorporated by reference in its entirety). The changes that take
place when triglyceride monomers are converted into polymer oils by
blowing has been summarized as follows: " . . . when linseed oil
was blown with air at temperatures ranging between 100 and
200.degree. and samples analyzed at intervals, the following facts
were apparent. The viscosity, saponification number, density, acid
number, hydroxyl number, and ethanol tolerance increased with an
increase in time and temperature and, in addition, the degree of
maturation and the drying time decreased . . . (189)" (Wexler, H.
Polymerization of Drying Oils, Chemical Reviews 64(6) 591-611,
1964, citing ber geblasene Leinole, Wilaborn and Morgner, Fette,
Siefen, Anstrichmittel 57 178181 (1955) which are hereby
incorporated by reference in their entirety). Inedible blown oils
have traditionally been used in applications such as stuffing
greases for leather, and applications in patent leather daubs,
lithography, ink, plasticizers, alkyd resins, coatings, varnishes,
caulks, putties, mastics, rust inhibitors, ceramic deflocculants,
and for lubricants in which traditional triglyceride monomer oils
would be less suitable. Blown Soya J-L.TM. is a blown soybean oil
commercially available from Werner G. Smith Company, Cleveland,
Ohio, USA.
[0040] Another method for polymerizing triglyceride monomers is by
heat processing an unsaturated natural oil with at least one
reactive comonomer such as styrene, vinyl toluene, maleic
anhydride, or dicyclopentadiene to form "copolymer oils"
(Copolymerization, J. Amer. Oil Chem. Soc. 27(11) 481-491 1950,
hereby incorporated by reference in its entirety). A mixture of
triglyceride monomers and reactive comonomer is heated to, for
example 75-135.degree. C., and may continue for 20-50 hours. Higher
temperatures may lead to gel formation United States (U.S. Pat. No.
2,382,213, issued Aug. 14, 1945, hereby incorporated by reference
in its entirety). Air or oxygen may be passed through the oil
during the process. Renewable-source-based copolymer oils such as
maleinized and dicyclopentadiene oils are characterized by a fast
drying time and water resistance. Blending such copolymer oils with
renewable oil monomer or modified oil monomers yields oil blends
that also possess characteristic properties and provides more
diversity of chemical properties. Toplin X-Z.TM. is a copolymer oil
available from Archer Daniels Midland Company, Decatur Ill.,
USA.
[0041] Each of polymer oils, combinations of polymer oils with
monomer oils, and macroinitiators may be partially or fully
hydrogenated to reduce the number of double bonds in the oils. The
term "hydrogenated" encompasses varying degrees of partial and full
hydrogenation. Conducting partial hydrogenation allows the oils to
retain some double bonds to provide useful sites for
derivatization. The properties of polymers made from partially
hydrogenated heat-bodied oils, blown oil, and/or copolymer oils can
be selected or tuned by controlling the degree of hydrogenation of
the oils. Careful selection of catalysts and conditions is
necessary when hydrogenating macroinitiators to prevent
displacement of the halogen component of the macroinitiator. A
description of methods suitable for hydrogenation of renewable
source-derived oils and fats is provided in the disclosure of
previously cited U.S. Pat. No. 7,842,746. Typically, iodine value
("IV,") is used to quantify the double bonds in a composition. The
IV of linseed oil triglyceride monomer varies from about 135 to
about 175; The IV of a polymer oil of linseed (heat bodied linseed
oil), for example, ranges from approximately 115-150. Although the
physical characteristics of the composition can be determined
empirically, the iodine values of the oil(s) can be used to
quantify double bonds for any given embodiment of the present
disclosure. When a triglyceride monomer, polymer oil, combination
of polymer oil with monomer oil, or macroinitiator is hydrogenated,
the IV of the composition decreases. Polymer oils or combinations
of polymer oils with monomer oils may be hydrogenated before
halogenation to provide a range of physical properties in block
copolymers made therefrom. The IV values of the macroinitiators
claimed herein may fall below about 110, in another embodiment
below about 70, and in still another embodiment below about 30.
[0042] Renewable source derived triglyceride monomers may be
subjected to certain reactions while maintaining their triglyceride
structure. For example, hydrogenation is commonly carried out and
removes double bonds. Polymer oils or halogenated polymer oil
macroinitiators can be blended with unmodified or modified
renewable source-derived fats and oil monomers. Further,
epoxidation may be carried out to attach oxygen heteroatoms to one
or more site of unsaturation of one or more fatty acid (fatty acyl)
chains of oil monomers. Blending such unmodified or modified
triglyceride monomers with polymerized oils or halogenated
polymerize oil macroinitiators yields oil blends that possess
characteristic properties and provide more diversity of chemical
properties.
[0043] The radical polymerization of monomer A and B to form
thermoplastic block copolymer can be performed through living free
radical polymerization which involves living/controlled
polymerization with free radical as the active polymer chain end
(Moad et al., "The Chemistry of Radical Polymerization-Second Fully
Revised Edition," Elsevier Science Ltd. (2006), which is hereby
incorporated by reference in its entirety). This form of
polymerization is a form of addition polymerization where the
ability of a growing polymer chain to terminate has been removed.
The rate of chain initiation is thus much larger than the rate of
chain propagation. The result is that the polymer chains grow at a
more constant rate than seen in traditional chain polymerization
and their lengths remain very similar. One form of living free
radical polymerization is atom transfer radical polymerization.
[0044] Atom transfer radical polymerization (ATRP) is a catalyzed,
reversible redox process that achieves controlled polymerization
via facile transfer of labile radicals (e.g., halide radicals)
between growing polymer chains and a catalyst (Davis et al., "Atom
Transfer Radical Polymerization of tert-Butyl Acrylate and
Preparation of Block Copolymers," Macromolecules 33:4039-4047
(2000); Matyjaszewski et al., "Atom Transfer Radical
Polymerization," Chemical Reviews 101:2921-2990 (2001), which are
hereby incorporated by reference in their entirety). In
conventional ATRP, chain termination and transfer reactions are
essentially eliminated by keeping the free radical concentration
small. Briefly, the mechanism by which ATRP operates may be
summarized as:
##STR00001##
[0045] In Equation (1), the labile radical X may be a halogen
(e.g., Br, Cl) attached to end of a polymer P. The catalyst, Cu'Br,
reversibly abstracts this halogen, forming a polymer free radical
(P.). The equilibrium achieved between inert polymers and active
polymer free radicals strongly favors the left side
(K<<10.sup.-8). Equation (2) is the standard free radical
propagation reaction between a polymer of length i and a monomer M.
The small free radical concentration ensured by equation (1)
virtually eliminates termination reactions, and the halogen
functionality is retained on polymers produced, which allows the
production of multiblock copolymers from nearly any monomer
amenable to conventional free radical polymerization.
[0046] The ATRP polymerization reaction starts with initiation.
Initiation is conventionally accomplished by adding an agent
capable of decomposing to form free radicals; the decomposed free
radical fragment of the initiator attacks a monomer yielding a
monomer-free radical, and ultimately produces an intermediate
capable of propagating polymerization. These agents often are
referred to as "initiators." The initiation is typically based on
the reversible formation of growing radicals in a redox reaction
between various transition metal compounds and an initiator.
Suitable initiators depend greatly on the details of the
polymerization, including the types of monomers being used, the
type of catalyst system, the solvent system and the reaction
conditions. Simple organic halides are typically used as model
halogen atom transfer initiators. The present invention obviates
the need for addition of a separate initiator.
[0047] For the polymerization of renewable source-derived oil or
fat polymer oil blocks, self-initiation takes place due to the
presence of the polymer oil macroinitiator, and a separate
initiator is not needed. Moreover, for vinyl aromatic blocks such
as styrene, thermal self-initiation can occur without the need for
additional initiators.
[0048] In ATRP, the introduction of a catalyst system to the
reaction media is required to establish the equilibrium between
active states (active polymer free radicals for the growth of the
polymer) and dormant states (the formed inert polymer). The
catalyst is typically a transition metal compound being capable of
participating in a redox cycle with the initiator and a dormant
polymer chain. The transition-metal compound used in conventional
ATRP is a transition-metal halide. Any transition metal that can
participate in a redox cycle with the initiator and dormant polymer
chain, but does not form a direct C-metal bond with the polymer
chain, is suitable in the present invention. The exemplary
transition metals include Cu.sup.1+, Cu.sup.2+, Fe.sup.2+,
Fe.sup.3+, Ru.sup.2+, Ru.sup.3+, Ru.sup.4+, Ru.sup.5+, Ru.sup.6+,
Cr.sup.+2, Cr.sup.+3, Mo.sup.0, Mo.sup.1+, Mo.sup.2+, MO.sup.3+,
W.sup.2+, W.sup.3+, Mn.sup.3+, Mn.sup.4+, Rh.sup.+, Rh.sup.2+,
Rh.sup.3+, Rh.sup.4+, Re.sup.2+, Re.sup.3+, Re.sup.4+, Co.sup.+,
Co.sup.2+, Co.sup.3+, V.sup.2+, V.sup.3+, V.sup.4+, V.sup.5+,
Zn.sup.+, Zn.sup.2+, Au.sup.+, Au.sup.2+, Au.sup.3+, Hg.sup.+,
Hg.sup.2+, Pd.sup.0, Pd.sup.+, Pd.sup.2+, Pt.sup.0, Pt.sup.+,
Pt.sup.2+, Pt.sup.3+, pt.sup.4+, Ir.sup.0, Ir.sup.+, Ir.sup.2+,
Ir.sup.3+, Ir.sup.4+, Os.sup.2+, Os.sup.3+, Os.sup.4+, Nb.sup.2+,
Nb.sup.3+, Nb.sup.4+, Nb.sup.5+, Ta.sup.3+, Ta.sup.4+, Ta.sup.5+,
Ni.sup.0, Ni.sup.+, Ni.sup.2+, Ni.sup.3+, Nd.sup.0, Nd.sup.+,
Nd.sup.2+, Nd.sup.3+, Ag.sup.+, and Ag.sup.2+. A typical
transition-metal catalyst system used herein is a copper (I)
halide. The ligand serves to coordinate with the transition metal
compound such that direct bonds between the transition metal and
growing polymer radicals are not formed, and the formed copolymer
material isolated. The ligand can be any N-, O-, P- or S-containing
compound that coordinates with the transition metal to form a
sigma-bond, any C-containing compound that coordinates with the
transition metal to form a pi-bond, or any C-containing compound
that coordinates with the transition metal to form a C-transition
metal sigma-bond but does not form a C--C bond with the monomers
under the polymerizing conditions. A typical ligand used herein is
pentamethyldiethylenetriamine (PMDETA).
[0049] The state of the art of ATRP has been reviewed
(Matyjaszewski et al.). More details for selection of initiators,
catalysts/ligand systems for ATRP reaction can be found in U.S.
Pat. No. 5,763,548 to Matyjaszewski et al. and U.S. Pat. No.
6,538,091 to Matyjaszewski et al., which are hereby incorporated by
reference in their entirety.
[0050] In ATRP of styrene and polymer oil macroinitiator to prepare
thermoplastic elastomers, polymerization can be carried out at a
temperature of 120.degree. C. or lower. The optimal temperature is
the minimum at which polymerization can occur over reasonable time
scales, e.g., 6-48 hours. In ATRP of polymer oil macroinitiators to
make elastomers, advantages of macroinitiators of high molecular
weight and a low glass transition temperature (T.sub.g), and with
the retention of the terminal halogen, allows the subsequent
addition of a polystyrene block. Thus, high reaction temperatures
as in conventional radical polymerizations are undesirable in ATRP
of polymer oil macroinitiators. A typical reaction temperature for
ATRP of styrene and BO, HBO or CPO macroinitiator oil is
140.degree. C. or lower.
[0051] Parenthetically, benzyl bromide or benzyl chloride can be
used as initiator in ATRP of styrene and polymer oil. CuX (where
X=Br or Cl) can be used as the catalyst system and PMDETA can be
used as the ligand. Typically, a 1:1 molar ratio of Cu.sub.IX:PX is
sufficient to establish the equilibrium between active and dormant
states of the resulting polymers. CuX.sub.2 can be used as a
counter-catalyst to further reduce the polymer free radical
concentration. Typically, a 0.1:1 molar ratio of
counter-catalyst:catalyst and a 1:1 molar ratio of ligand:(catalyst
and counter-catalyst) are desirable to ensure the solvation of the
catalyst. The molecular weight of the resulting polymer is governed
in part through the ratio, which may vary between 5:1 to
1000:1.
[0052] In the present invention, the degree of halogenation of a
polymer oil dictates the number of macroinitiator sites, the
molecular weight of resulting multiblock copolymers can be adjusted
by adjusting the number of macroinitiation sites, the weight of
monomer A, and the length of the polymerization reaction.
[0053] A solvent for the ATRP reaction is selected based the
requirements of mutual polymer oil macroinitiator/polystyrene
solubility and a normal boiling point compatible with the
polymerization temperature. The solvent used in the ATRP of styrene
and polymer oil macroinitiator may be toluene, THF, chloroform,
cyclohexane, or a mixture thereof. A typical solvent used for ATRP
of styrene and polymer oil macroinitiator oil is toluene. Monomer
and macroinitiator concentration in the reactions depend partially
on the solubility of the monomer, macroinitiator, and the polymer
products as well as the evaporation temperature of the solvent. The
concentration of monomers and macroinitiators dissolved in the
solvent in the ATRP reactions may range from 5% to 100% (by weight
of the sum of the monomers and the macroinitiator). Typically, the
sum of monomer and macroinitiator concentrations in the solvent is
less than 50% by weight to ensure the solubility of the resulting
polymers and additionally to prevent premature gelation.
[0054] Controlled radical polymerization such as ATRP limits the
number of initiation sites, drastically reduces the rate of chain
transfer and termination reactions, and also introduces the
capability to produce custom chain architectures such as block
copolymers (BCPs). An advantage of applying ATRP to the
polymerization of radically polymerizable renewable source-derived
polymer oil macroinitiator containing one or more polymer oils is
that the initiation of new chain branches from other growing chains
is hindered. However, chain branching ultimately leading to
gelation is still possible, and will proceed quickly if the
polymerization rate or polymer concentration becomes too large.
When the reactivities of a propagating chain towards all functional
sites on both free monomers and repeating units that are already
incorporated into a chain are identical, the general expectation is
that the gel point will be reached at an extremely low conversion,
such that, prior to gelation, the polymer of radically
polymerizable renewable source-derived polymer oil macroinitiator
containing one or more polymer oils has not yet achieved a degree
of polymerization sufficient for useful mechanical properties to
develop. This general expectation is supported by the past two
decades of reports of thermosets from vegetable oils produced by
conventional cationic and free radical polymerization.
[0055] In conventional ATRP, the introduction of Cu.sub.IX to the
reaction media is required to establish the equilibrium between
active and dormant states. Typically, a 1:1 molar ratio of
Cu.sub.IIX:PX is sufficient to establish this equilibrium
(Matyjaszewski et al., 2001). In some conventional systems, the
equilibrium falls too far to the right and polymerization is
uncontrolled unless the counter catalyst, Cu.sub.IIX.sub.2, is
introduced to control the equilibrium, which is independent of the
reaction temperature (Behling et al., "Influence of Graft Density
on Kinetics of Surface-Initiated ATRP of Polystyrene from
Montmorillonite," Macromolecules 42:1867-1872 (2009); Behling et
al., "Hierarchically Ordered Montmorillonite Block Copolymer
Brushes," Macromolecules, 43(5): 2111-2114 (2010), which are hereby
incorporated by reference in their entirety).
[0056] The present invention encompasses the discovery that
halogenated polymer oils can be synthesized, and that they are
useful as macroinitiators in ATRP. In the present invention,
polymer oils or hydrogenated polymer oils are halogenated to form
polymer oil macroinitiators having a halogen polymerization
initiator incorporated into the B monomer. The halogen serves as an
initiation site for polymerization to make block copolymers. The
ratio of styrene monomer to macroinitiator sites on the polymer oil
determines the molecular weight of the polystyrene block and can be
adjusted to control the properties of block copolymers made
therefrom.
[0057] Polymer oils or hydrogenated polymer oils made from
renewable oils can be halogenated directly. When a polymer oil or
hydrogenated polymer oil is halogenated, the halogen bound to the
polymer oil serves as an initiation site for multiblock
copolymerization. Suitable macroinitiator embodiments include a
halogenated heat-bodied oil, a halogenated blown oil, a halogenated
copolymer oil, a halogenated hydrogenated heat-bodied oil, a
halogenated hydrogenated blown oil, and a halogenated hydrogenated
copolymer oil. The ratio of polymer oil to halogen initiator sites
determines the number of initiation points for formation of
polystyrene blocks.
[0058] The quantities of initiator sites in the macroinitiators of
the present invention can be controlled to adjust the properties of
multiblock copolymers made from the macroinitiators.
Macroinitiators having a higher number of halogen initiation sites
per polymer oil can produce hard, glassy polymers useful as impact
modifiers. Macroinitiators having a lower number of halogen
initiation sites per polymer oil can produce solid rubbery type
thermoplastic materials, with or without tackiness, and can be
thermosetting under the proper conditions. To achieve a multiblock
copolymer with rubber-like properties, the number of
macroinitiation sites on the macroinitiator B block can be lower,
or the polymer oil may be present as the majority phase. By using
halogenated polymer oil as greater than half of the mass, the
resulting high critical entanglement molecular weight provides a
polystyrene-based block copolymer with desired properties.
[0059] The formation of the macroinitiator by halogenation can take
place on any of at least three functional groups in polymer oil. In
a first embodiment, fatty acid double bonds remaining after
formation of the polymer are halogenated to form a macroinitiator.
In a second embodiment, the macroinitiator is formed by
halogenation of hydroxyl groups present in the polymer oil. In a
third embodiment, alpha carbons of fatty acid moieties in polymer
oils can be halogenated.
[0060] One measure of the molecular weight of a polymer is "Mn",
which is the total weight of all the polymer molecules in a sample,
divided by the total number of polymer molecules in the sample.
[0061] In a typical SBS elastomer, the styrene composition is about
10-30 wt % such that spherical or cylindrical styrene domains form
in a matrix of butadiene. When the temperature is below the glass
transition temperature of polystyrene (T.sub.g=100.degree. C.), the
polybutadiene matrix is liquid (T.sub.g<-90.degree. C.) but is
bound between the vitreous polystyrene spheres, which serve as
physical crosslinks. When the temperature is above the glass
transition temperature of polystyrene, the entire elastomer system
is molten and may be processed easily. Crosslinked poly(soybean
oil) has been reported to have T.sub.g values as low as -56.degree.
C. (Yang et al., "Conjugation of Soybean Oil and Its Free-Radical
Copolymerization with Acrylonitrile," Journal of Polymers and the
Environment 1-7 (2010), which is hereby incorporated by reference
in its entirety).
[0062] Another aspect of the present invention relates to a method
of preparing a thermoplastic block copolymer. The method comprises
providing a radically polymerizable monomer, represented by A, or a
polymer block PA comprising one or more units of monomer A. A
radically polymerizable component B derived from a renewable
source-derived oil or fat polymer oil macroinitiator, is also
provided. Monomer A or the polymer block PA is then radically
polymerized with component B, in the presence of the renewable
source-derived oil or fat polymer oil macroinitiator and a
transition-metal catalyst system to form the thermoplastic block
copolymer.
[0063] After the radical polymerization, the polymerized renewable
source-derived oil or fat-based block copolymer may be further
catalytically hydrogenated to partially or fully saturate the
renewable source-derived polymer oil block. This process removes
reactive unsaturation from the rubbery component, yielding improved
resistance to oxidative degradation, reduced crosslinkability and
increased resistance to chemical attack. If carried out under
selected conditions, hydrogenation may remove any remaining free
halogen from the macroinitiator, promoting increased resistance to
chemical attack.
[0064] Exemplary procedures for synthesizing poly(heat bodied oil)
(PHBO), poly (blown oil, PBO) and poly(copolymer oil, PCPO) via
ATRP with a polymer oil macroinitiator are presented in the
examples which follow.
[0065] The degree of polymerization of polymer oil B multiblocks
can be determined by gel permeation chromatography. The
polymerization kinetics can be subsequently assessed and the
parameters may be fine-tuned such that B blocks derived from
polymer oil compounds can be reproducibly produced with minimal
polydispersity and of targeted molecular weight. Parenthetically,
the ratio of weight average molecular mass to the number average
molecular mass is called polydispersity index, PDI, and is a
measure of homogeneity of a polymer. In monodisperse polymers, the
value of PDI is one. Polydisperse polymers have a wide range of
molecular weights, so the value of PDI is greater than one.
Differential scanning calorimetry is typically used to assess the
glass transition temperatures (T.sub.g) of polymers.
[0066] A further aspect of the present invention relates to a
thermoplastic polymer comprising one or more units of a radically
polymerizable renewable source-derived polymer oil or fat monomer
containing one or more triglycerides. All above embodiments
described for the PB block, such as compositions, structures,
physical and chemical properties (e.g., molecular weight, glass
transition temperature, etc.) are equally suitable for the
polymerizable renewable source-derived polymer oil or fat-based
thermoplastic polymers.
[0067] Another aspect of the present invention relates to a method
of preparing a thermoplastic polymer or polymer block. The method
comprises providing a radically polymerizable renewable
source-derived polymer oil or fat macroinitiator containing one or
more triglycerides. This renewable source-derived polymer oil or
fat macroinitiator is then radically polymerized, in the presence
of a transition-metal forming the catalyst system with the
macroinitiator to form the thermoplastic polymer or polymer block.
This thermoplastic polymer can itself be used as a thermoplastic
elastomer. Alternatively, this thermoplastic polymer can be used as
a polymer block, and can be further polymerized with other monomers
to form a polymerized renewable source-derived polymer oil or
fat-based thermoplastic block copolymer. All above embodiments
described for methods of preparing the PB block, including reaction
steps and reaction conditions (e.g., reaction reagents, catalyst
systems, macroinitiators, temperatures, solvents, initiation and
termination of the reaction, etc.) are suitable also for producing
the polymerizable renewable source-derived polymer oil or fat-based
thermoplastic polymers.
[0068] Other aspects of the present invention relate to the use of
the polymerized renewable source-derived polymer oil or fat-based
multiblock copolymers in a variety of applications. As exemplified
below, the processes of the present invention can be controlled to
produce hard, glassy polymers, thermosetting (crumb rubber)
elastomers, or tacky type elastomers as desired. Exemplary
applications of the block copolymers of the present invention
include their use: as rubbers or elastomers; as toughened
engineering thermoplastics; as asphalt modifiers; as resin
modifiers; as engineering resins; as leather and cement modifiers;
in footwear, such as in rubber shoe heels, rubber shoe soles; in
automobiles, such as in tires, hoses, power belts, conveyor belts,
printing rolls, rubber wringers, automobile floor mats, mud flaps
for trucks, ball mill liners, and weather strips; as adhesives,
such as pressure sensitive adhesives; in aerospace equipment; as
viscosity index improvers; as detergents; as diagnostic agents and
supports therefore; as dispersants; as emulsifiers; as lubricants
and/or surfactants; as paper additives and coating agents; and in
packaging, such as food and beverage packaging materials.
[0069] Uses for crumb rubber include flooring and rubber mats,
highway construction and repair, recreation areas, auto bumpers,
floor mats and liners, artificial athletic surfaces,
stress-absorbing membrane interlayers, open-graded friction
courses, paver placed surface seal, gap-graded mixtures, stone
matrix asphalt, and crumb rubber modified asphalt (CRMA). CRMA,
when added to asphalt, can impart improved resistance to oxidation,
rutting, raveling, delamination and cracking.
[0070] In another aspect, a composition is provided comprising a
polymerization macroinitiator, wherein the polymerization
macroinitiator comprises at least one halogenated polymer oil
selected from the group consisting of halogenated heat-bodied oil,
a halogenated blown oil, a halogenated copolymer oil, a halogenated
hydrogenated heat-bodied oil, a halogenated hydrogenated blown oil,
a halogenated hydrogenated copolymer oil, and combinations of any
thereof, wherein the polymer oil comprises at least one renewable
source-derived oil or fat.
[0071] In another embodiment, a method for making the
polymerization macroinitiator is provided, wherein a polymer oil
having at least one double bond is halogenated. The halogenation
may be carried out with the acid of a halogen to form a halogenated
polymer oil macroinitiator. The halogenated sites in the oil can
function as macroinitiators in subsequent polymerization,
exemplified by Atom Transfer Radical Polymerization (ATRP) with
styrene.
[0072] In an alternative embodiment, a method for making the
polymerization macroinitiator is provided by halogenation of free
hydroxyl groups of polymerized oil formed during oil polymerization
(heat-bodying oil, blowing oil, or forming copolymer oil) is
carried out with a halogenated acylhalogen, exemplified by
bromoacetyl chlorine or bromoacetyl bromine. Free hydroxyl groups
may be formed from double bonds in the fatty acyl chain or at the
glycerol moiety of oils by the hydrolysis of an ester bond between
the glycerol and the fatty acyl chain.
[0073] In yet another embodiment, a method for making the
polymerization macroinitiator is provided by halogenation at alpha
carbons of component fatty acid moieties.
[0074] In a further embodiment, the polymer oil is made from a
renewable source derived fat or oil selected from the group
consisting of algal oil, animal fat, beef tallow, borneo tallow,
butterfat, camelina oil, candlefish oil, canola oil, castor oil,
cocoa butter, cocoa butter substitutes, coconut oil, cod-liver oil,
colza oil, coriander oil, corn oil, cottonseed oil, false flax oil,
flaxseed oil, float grease from wastewater treatment facilities,
hazelnut oil, hempseed oil, herring oil, illipe fat, jatropha oil,
kokum butter, lanolin, lard, linseed oil, mango kernel oil, marine
oils, meadowfoam oil, menhaden oil, microbial oil, milk fat, mowrah
fat, mustard oil, mutton tallow, neat's foot oil, oiticica oil,
olive oil, orange roughy oil, palm oil, palm kernel oil, palm
kernel olein, palm kernel stearin, palm olein, palm stearin, peanut
oil, phulwara butter, pile herd oil, plant oil, pork lard, radish
oil, ramtil oil, rapeseed oil, rice bran oil, safflower oil, sal
fat, salicornia oil, sardine oil, sasanqua oil, sesame oil, shea
fat, shea butter, single-cell oil, soybean oil, sunflower seed oil,
tall oil, tallow, tigernut oil, tsubaki oil, tung oil,
triacylglycerols, triolein, used cooking oil, vegetable oil, walnut
oil, whale oil, white grease, yellow grease, and derivatives,
conjugated derivatives, genetically-modified derivatives, and
combinations of any thereof.
[0075] In another embodiment, the polymer oil is made from a
renewable source derived fat or oil containing one or more
conjugated fatty acids selected from the group consisting of
conjugated linoleic acids, rumenic acid (9-cis,
11-trans-octadecadienoic acid), 10-trans, 12-trans-octadecadienoic
acid, 10-trans, 12-cis-octadecadienoic acid, conjugated linolenic
acid, alpha-eleostearic acid (9-cis, 11-trans, 13-trans
octadecatrienoic acid), beta-eleostearic acid (9-trans, 11-trans,
13-trans octadecatrienoic acid), rumelenic acid
(9-cis,11-trans,15-cis-octadecatrienoic acid), punicic acid
(9-cis,11-trans,13-cis-octadecatrienoic acid), catalpic acid
(9-trans, 11-trans, 13-cis-octadecatrienoic acid), alpha-calendic
acid (8-trans, 10-trans, 12-cis octadecatrienoic acid),
beta-calendic acid (8-trans, 10-trans, 12-trans octadecatrienoic
acid), jacaric acid (8-cis, 10-trans, 12-cis octadecatrienoic
acid), tetraenoic acids, alpha-parinaric acid
(9-trans,11-cis,13-cis, 15-trans-octadecatetraenoic acid),
beta-parinaric acid (9-trans,11-trans,13-trans,
15-trans-octadecatetraenoic acid), 2-trans, 4-trans, 6-trans,
11-cis octadecatetraenoic acid from rhibozium bacteria, pentaenoic
acids, bosseopentaenoic acid (5-cis, 8-cis, 10-trans, 12-trans, 14
cis-pentaenoic acid), hexaenoic acid, 4-cis, 7-cis, 9-trans,
13-cis, 16-cis, 19-cis docosahexaenoic acid from marine algae, and
combinations of any thereof.
[0076] In another embodiment, a polymer made from polymerization
macroinitiator comprising halogenated renewable source derived
polymer oils is taught, wherein the macroinitiator comprises at
least one of halogenated heat-bodied oil, a halogenated blown oil,
a halogenated copolymer oil, a halogenated hydrogenated heat-bodied
oil, a halogenated hydrogenated blown oil, a halogenated
hydrogenated copolymer oil, and combinations of any thereof. In an
embodiment, the polymer comprises a hard glassy polymer. In an
embodiment, the hard glassy polymer comprises an impact modifier.
In a further embodiment, the impact modifier can be incorporated
into at least one of molded plastic, extruded plastic,
acrylonitrile butadiene styrene, polyvinyl halide products, nylons,
polyesters, polypropylene alloys, chlorinated polyethylenes,
polycarbonates, polystyrenes, acrylics, and combinations of any
thereof. In another embodiment, the polymer comprises a thermoset
polymer. In a further embodiment, the thermoset polymer is suitable
for use in an application selected from the group consisting of
flooring, rubber mats, highway construction, highway repair,
recreation areas, automobile bumpers, automobile floor mats,
automobile liners, tires, hoses, power belts, conveyor belts,
artificial athletic surfaces, stress-absorbing membrane
interlayers, open-graded friction courses, paver placed surface
seal, gap-graded mixtures, stone matrix asphalt, crumb rubber
modified asphalt, toughened engineering thermoplastics, asphalt
modifiers, resin modifiers, engineering resins, leather and cement
modifiers, in footwear, in rubber shoe heels, rubber shoe soles, in
printing rolls, rubber wringers, mud flaps for trucks, ball mill
liners, weather strips, adhesives, pressure sensitive adhesives, in
aerospace equipment, as viscosity index improvers, detergents,
diagnostic agents, dispersants, emulsifiers, lubricants,
surfactants, paper additives, coating agents, paper coating agents,
food packaging, beverage packaging, and combinations of any
thereof. In yet another embodiment, the polymer comprises a
thermoplastic elastomer. In a further embodiment the thermoplastic
elastomer may be incorporated into at least one of binders, asphalt
binders, tackifiers, flooring, rubber mats, highway construction,
highway repair, recreation areas, automobile bumpers, automobile
floor mats, automobile liners, tires, hoses, power belts, conveyor
belts, artificial athletic surfaces, stress-absorbing membrane
interlayers, open-graded friction courses, paver placed surface
seal, gap-graded mixtures, stone matrix asphalt, crumb rubber
modified asphalt, toughened engineering thermoplastics, asphalt
modifiers, resin modifiers, engineering resins, leather and cement
modifiers, in footwear, in rubber shoe heels, rubber shoe soles, in
printing rolls, rubber wringers, mud flaps for trucks, ball mill
liners, weather strips, adhesives, pressure sensitive adhesives, in
aerospace equipment, as viscosity index improvers, detergents,
diagnostic agents, dispersants, emulsifiers, lubricants,
surfactants, paper additives, paper coating agents, food packaging,
beverage packaging, and combinations of any thereof. In a still
further embodiment, the polymer may comprise comprises at least one
A block made from monomers selected from the group consisting of
styrene, alpha-methyl styrene, t-butyl styrene, vinyl xylene, vinyl
naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate,
C1-C6 (meth)acrylate, methyl methacrylate, ethyl methacrylate,
propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate,
hexyl (meth)acrylate), acrylonitrile, adiponitrile,
methacrylonitrile, butadiene, isoprene, a vinyl aromatic monomer, a
polystyrene homopolymer, and combinations of any thereof. In yet
another embodiment, the polymer may be further subjected to
vulcanization, crosslinking, compatibilizing, compounding with one
or more other materials, and combinations of any thereof.
[0077] In one embodiment of the present invention, the
thermoplastic and elastomeric block copolymer has a PA-PB
multiblock polymer architecture, where the PA block is a
linear-chain polystyrene (PS) and the PB multiblock is a polymer
oil (PO) or radicals thereof. The PO may be at least one of a blown
oil (BO), a heat-bodied oil (HBO), a copolymer oil (CPO) a
hydrogenated blown oil (BO), a hydrogenated heat-bodied oil (HBO),
or a hydrogenated copolymer oil (CPO). The PS-PO di-block copolymer
thus has an elastomeric block comprising a B multiblock made from a
polymer oil macroinitiator, and one PS block bonded to one
macroinitiation site of the PO B block. The block copolymer has a
molecular weight (Mn) ranging from 1 kDa to 500 kDa, for instance,
from about 10 kDa to 300 kDa, from about 40 to about 100 kDa, or
from about 80 to about 100 kDa and a first glass transition
temperature (T.sub.g) below -15.degree. C., for instance, from
about -60.degree. C. to about -20.degree. C.
[0078] In one embodiment of the present invention, the
thermoplastic and elastomeric block copolymer has a PA-PB-PA
triblock polymer architecture, where the PA block is a linear-chain
polystyrene (PS), and the PB multiblock is a polymer oil (PO) or
radical thereof. This polymer oil-based styrenic triblock copolymer
(PS-PO-PS) thus has an elastomeric interior block comprising a B
multiblock made from a polymer oil macroinitiator having PS blocks
bonded to two macroinitiation sites, and a thermoplastic outer
block PS formed bonded to two macroinitiation sites of the interior
block PO. The PS-PO-PS tri-block copolymer has a molecular weight
ranging from 7 kDa to 1000 kDa, for instance, from about 7 kDa to
about 500 kDa, from about 15 kDA to about 350 kDa, from about 80
kDa to about 120 kDa or from about 100 kDa to about 120 kDa. The
triblock copolymer may have a first T.sub.g below -15.degree. C.,
for instance, from about -60.degree. C. to about -28.degree. C.
[0079] In another embodiment of the present invention, the
thermoplastic and elastomeric block copolymer has a multiblock
polymer architecture comprising three or more PA blocks comprising
linear-chain polystyrenes (PS), and the PB multiblock is a polymer
oil (PO) or radical thereof having at least three macroinitiation
sites. This polymer oil-based styrenic multiblock copolymer thus
has an elastomeric interior block comprising a B multiblock made
from a polymer oil macroinitiator, and three or more thermoplastic
outer PS blocks formed bonded to the interior multiblock PO.
[0080] In one embodiment, the radical polymerizing is carried out
by atom transfer radical polymerization with a polymer oil
macroinitiator. The polymer oil is selected from at least one of a
halogenated blown oil (BO), a halogenated heat-bodied oil (HBO), a
halogenated copolymer oil (CPO), a halogenated hydrogenated blown
oil (BO), a halogenated hydrogenated heat-bodied oil (HBO), and a
halogenated hydrogenated copolymer oil (CPO).
[0081] In an alternative embodiment of the present invention, a
block copolymer derived from a renewable source derived fat or oil
comprises an impact modifier useful in molded plastic, extruded
plastic, PVC products, nylons, polyesters, polypropylene alloys,
chlorinated polyethylenes, polycarbonates, polystyrenes, and
acrylics.
[0082] Some embodiments of the present invention relate to methods
of making a thermoplastic multiblock copolymer comprising at least
one polymer block of radically polymerizable monomer and a polymer
block of radically polymerized renewable source-derived polymer oil
or fat containing one or more triglyceride polymer oils, according
to the above-described steps. The A block radically polymerizable
monomers used in this method include, but are not limited to,
styrene, a-methyl styrene, t-butyl styrene, vinyl, vinyl xylene,
vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl
acrylate, C1-C6 (meth)acrylate (i.e., methyl methacrylate, ethyl
methacrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl
(meth)acrylate, or hexyl (meth)acrylate), acrylonitrile,
adiponitrile, methacrylonitrile, butadiene, isoprene, a vinyl
aromatic monomer, a polystyrene homopolymer, a diolefin, a nitrile,
a dinitrile, or mixtures thereof. In one embodiment, the
polymerized vinyl monomer is a vinyl aromatic monomer, for
instance, a polystyrene homopolymer. In one embodiment, the polymer
oil macroinitiator is made from blown oil. The polymer oil
macroinitiator is made from a polymer oil.
[0083] Alternatively, the method of the present invention may
comprise the following steps: a) ATRP of styrene homopolymer (PS),
using a polymer oil derived macroinitiator in a solvent suitable
for the mutual dissolution of PS and the macroinitiator, to yield a
multiblock copolymer. In one embodiment, the method is carried out
in the presence of a solvent, without a counter-catalyst. The
polymerization can be carried out at a temperature ranging from 65
to 120.degree. C. The solvent concentration can range from 5% to
90% by mass ratio of the solvent to the macroinitiator B.
[0084] In some embodiments, the polymerized renewable
source-derived polymer oil-based multiblock copolymers of the
present invention can be used as a main component in a
thermoplastic elastomer composition, to improve the thermoplastic
and elastic properties of the composition. To form an elastomeric
composition, the multiblock copolymer can be further vulcanized,
cross-linked, compatibilized, and/or compounded with one or more
other materials, such as other elastomers, additives, modifiers
and/or fillers. The resulting elastomer can be used as a rubber
composition, in various industries such as in footwear,
automobiles, packaging, etc.
[0085] In one particular embodiment of one of the above-mentioned
possible applications, the polymerized renewable source-derived
polymer oil based multiblock copolymers of the present invention
can be used in an asphalt composition, as an asphalt additive,
modifier and/or filler at from 1 to 5 weight percent of the
composition. The asphalt composition may further comprise a bitumen
component.
[0086] In another particular embodiment, the polymerized renewable
source-derived polymer oil based block copolymers can be used in a
toughened engineering thermoplastic composition. These toughened
engineering thermoplastic composition typically comprise
predominantly a glassy or semi-crystalline component with a
minority of a rubbery or elastomeric component to increase the
toughness (reduce the brittleness) of the material, e.g. analogous
to High-Impact Polystyrene (HIPS). To form a toughened engineering
thermoplastic composition, the multiblock copolymer of the present
invention may be formulated such that the renewable source-derived
polymer-oil block is a minority component and serves to absorb
energy that would otherwise lead to the fracture of the solid
matrix. The block copolymer in the toughened engineering
thermoplastic composition may be further compounded as is
conventional with other materials, such as other engineering
thermoplastics, additives, modifiers, or fillers.
[0087] All the above embodiments described for applications of the
polymerized renewable source-derived polymer oil or fat-based
thermoplastic block copolymers are also suitable applications of
the renewable source-derived polymer oil based thermoplastic
polymers.
[0088] The present invention is further demonstrated by the
non-limiting examples that follow:
EXAMPLES
Example 1
[0089] Synthesis of a Heat-Bodied Linseed Oil Macroinitiator
[0090] Heat-bodied linseed oil (20 g) (OKO M25, ADM Red Wing Minn.)
were combined with 33% hydrobromic acid in acetic acid (37 mL)
(Aldrich) and toluene (20 mL) (Fisher) in a 100 mL round bottom
flask. The mixture was stirred at room temperature with a magnetic
stir bar and stir plate under a nitrogen atmosphere for 18 h to
halogenate the heat-bodied linseed oil. After the halogenation, the
mixture was washed three times with water and the toluene was
removed by rotary evaporation. The resulting brominated oil was
characterized by 1H-NMR and was found to have 1.32 bromine per
triglyceride repeat unit.
Example 2
[0091] Atom Transfer Radical Polymerization Synthesis of
Styrene/Polymer Oil Copolymer Using a Polymer Oil Macroinitiator to
Form Hard Glassy Polymers.
[0092] Various ratios of halogenated polymer oil (polymerized
linseed oil) macroinitiator, styrene, copper(I) chloride, copper
metal, pentamethyldiethylene triamine were combined with 20 mL
toluene in a 100 mL Schlenk flask (Table 2.1). No halogen initiator
was added to the reaction mixtures. The reaction mixtures were
subjected to three freeze/pump/thaw cycles to remove oxygen (frozen
with liquid nitrogen, pumped down to 133.322 Pascal (1 torr)
pressure, sealed with the stopcock and allowed to thaw). The flask
was then flushed with nitrogen through a nitrogen line equipped
with a bubbler. Each reaction mixture was stirred with a magnetic
stir bar on a stir plate and heated to 110.degree. C. for 16 h to
conduct atom transfer radical polymerization. After the reaction,
the product mixtures were poured into stirring methanol to
precipitate the resulting polymer and the polymer was collected by
filtration. The solid polymer was then redissolved in methylene
chloride and filtered to remove the copper. The filtrate was then
poured into stirring methanol to precipitate the polymer. The
polymer was collected by filtration and dried under vacuum.
TABLE-US-00001 TABLE 2.1 Components of polymerization of
halogenated heat-bodied linseed oil. BrBLO = Brominated OKO M25
.TM. Heat-bodied linseed oil; CuCl = Copper(I) chloride; PMDETA =
pentamethyldiethylenetriamine. BrBLO Styrene CuCl PMDETA Run (g)
(mL) (g) Cu (mL) 1 1.0442 3.3546 0.1148 0.0775 0.5093 2 0.6677
3.8070 0.0370 0.0440 0.2890 3 0.3871 3.9862 0.0180 0.0307
0.2017
[0093] In this example, polymerization of halogenated heat-bodied
linseed oil took place without an added initiator, such as bromine.
The resulting polymers from runs 1-3 were hard glassy polymers at
ambient temperatures, potentially useful as impact resistant
polymers (like acrylonitrile butadiene styrene, ABS) or impact
modifiers to increase the durability of molded or extruded plastics
by reducing low temperature embrittlement in PVC products, nylons,
polyesters, polypropylene alloys, chlorinated polyethylenes,
polycarbonates, polystyrenes, and acrylics.
Example 3
[0094] Synthesis of Macroinitiator and Atom Transfer Radical
Polymerization Synthesis of Styrene/Polymer Oil Copolymer Using the
Polymer Oil Macroinitiator to Form Thermoplastic Crumb Rubbers and
Thermoset Polymers.
[0095] Heat-bodied linseed oil (OKO M37.TM., 20 g) was brominated
substantially as described in example 1, except 0.8 mL 33%
hydrobromic acid in acetic acid (37 mL) and 100 mL toluene were
used. The mixture was refluxed and stirred under a nitrogen
atmosphere for 2 h, then washed three times with water and the
toluene removed by rotary evaporation. The resulting brominated oil
was characterized by 1H-NMR and was found to have 0.35 bromine per
triglyceride repeat unit (by 1H-NMR).
[0096] Polymerization
[0097] The brominated heat-bodied vegetable oil was polymerized by
ATRP substantially as outlined in Example 2 with varying ratios of
halogenated polymerized linseed oil, styrene, copper(I) chloride,
copper metal, pentamethyldiethylene triamine (Table 3.1).
TABLE-US-00002 TABLE 3.1 Components of polymerization of
halogenated heat-bodied linseed oil. BrBLO = Brominated OKO M25
.TM. Heat-bodied linseed oil; CuCl = Copper(I) chloride; PMDETA =
pentamethyldiethylenetriamine. BrBLO Styrene CuCl PMDETA Run (g)
(mL) (g) Cu (mL) 4 3.1143 0.9744 0.1092 0.0225 0.1228 5 2.5497
1.5954 0.0732 0.0184 0.1005 6 2.1584 2.0259 0.0525 0.0156
0.0851
[0098] Copolymerization of brominated heat-bodied linseed oil
macroinitiator and styrene by ATRP under these conditions resulted
in thermoplastic solid rubbery type materials suitable for crumb
rubber applications. Greater than 50% of the mass originated from
the brominated heat-bodied linseed oil. The copolymers retained the
drying properties of the bodied linseed oil and crosslinked on
overnight exposure to air to make thermoset elastomers.
Example 4
[0099] Synthesis of Macroinitiator and Atom Transfer Radical
Polymerization Synthesis of Styrene/Polymer Oil Copolymer Using the
Polymer Oil Macroinitiator to Form Tacky Thermoplastic
Elastomers
[0100] Heat-bodied linseed oil (OKO M37.TM., 20 g) was brominated
substantially as described in example 1, except 0.35 mL 33%
hydrobromic acid in acetic acid (37 mL) and 100 mL toluene were
refluxed in a 250 mL round bottom flask with a magnetic stir bar
and stir plate under a nitrogen atmosphere for 2 h. The mixture was
then washed three times with water and the toluene removed by
rotary evaporation. The resulting brominated oil was characterized
by 1H-NMR and was found to contain 0.1 bromine per triglyceride
repeat unit.
[0101] Polymerization
[0102] The brominated heat-bodied vegetable oil was polymerized
substantially as outlined in Example 2 with varying ratios of
halogenated polymerized linseed oil, styrene, copper(I) chloride,
copper metal, and PMDETA. The reaction mixtures were poured into
stirring methanol to precipitate the resulting polymers and the
polymers collected by filtration. The solid polymers were then
redissolved in varying amounts of toluene and 100 ppm of
antioxidant (Butylated hydroxytoluene, BHT) was added (Table 4.1).
Number Average Molecular Weight (Mn) and Polydispersity Index (PDI)
were determined by gel permeation chromatography. Glass transition
temperature (Tg) was determined by Differential Scanning
calorimetry (Table 4.2).
TABLE-US-00003 TABLE 4.1 Components of polymerization of
halogenated heat-bodied linseed oil. BrBLO = Brominated OKO M25
.TM. Heat-bodied linseed oil; CuCl = Copper(I) chloride; PMDETA =
pentamethyldiethylenetriamine. BrBLO Styrene CuCI PMDETA Toluene
Run (g) (mL) (g) (mL) (mL) 7 3.1523 0.97 0.10506 0.15 16.70 8
2.5511 1.60 0.07638 0.12 13.51 9 2.1622 2.00 0.05400 0.10 11.45
TABLE-US-00004 TABLE 4.2 Characteristics of starting material
polymers produced in runs 7-9. Starting material = Brominated OKO
M25 .TM. Heat-bodied linseed oil; Mn g/mol = Number Average
Molecular Weight; PDI = Polydispersity index; Tg = Glass transition
temperature. 1st T.sub.g 2.sup.nd T.sub.g Run Description
<M.sub.n> g/mol PDI (.degree. C.) (.degree. C.) Starting
8,300 9.21 NA NA material 7 Thermoplastic 10,300 6.19 -29 T.sub.m
at 66 elastomer (Tacky solid) 8 Thermoplastic 13,200 4.95 -24 76
elastomer (rubbery solid 9 Thermoplastic 13,400 4.37 -25 80
elastomer (rubbery solid)
[0103] In the polymers described in this example, greater than 50%
of the mass originated from the brominated heat-bodied linseed oil.
Copolymerization of brominated heat-bodied linseed oil
macroinitiator and styrene by ATRP under these conditions resulted
in tacky thermoplastic elastomers or solid rubbery type materials
suitable for melt processing into finished goods. These properties
could be selected by adjusting the ratio of styrene to the
renewable source derived polymer oil macroinitiator. By decreasing
the ratio of a monomer (styrene) to the B multiblock, tackifiers
with a wide range of potential applications were formed. In
polymers formed with a higher ratio of A monomer to the B
macroinitiator, thermoplastic elastomers were formed as in Example
3, but the crosslinking and formation of thermoset elastomers was
prevented by the addition of an antioxidant (BHT).
* * * * *