Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-11-12
2001-04-03
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S093000, C527S300000, C527S305000, C527S311000, C521S084100, C521S151000
Reexamination Certificate
active
06211315
ABSTRACT:
FIELD OF THE INVENTION
This invention relates generally to the synthesis of thermoset plastics from biological oils. Particularly, this invention relates to polymerization of biological oils, such as soybean oil and fish oil, and to copolymerization of these oils with various olefins, to produce plastics from renewable resources.
BACKGROUND OF THE INVENTION
The natural environment is being overwhelmed by non-biodegradable, petroleum-based polymeric materials. The ever-increasing demand for such materials has increased dependence on petroleum products and left landfills overflowing with non-renewable, indestructible materials. The great current interest in cheap, biodegradable polymeric materials has recently encouraged the development of such materials from readily available, inexpensive natural sources, such as carbohydrates, starches and proteins, but relatively little work has been done on the conversion of fats and oils to such materials. The development of polymeric materials from biological oils, such as vegetable and fish oils, could dramatically expand and diversify the market for biological oils, while also improving the environment and reducing dependence on petroleum products.
Vegetable oils and fish oils are readily available in large quantities throughout the world. Of all biological oils, soybean oil is probably the most preferable oil for industrial use because it is inexpensive and produced in extremely large volume.
Soybean oil is principally composed of three unsaturated fatty acids: oleic acid, linoleic acid (also called linolic acid), and linolenic acid. These three fatty acids are the primary unsaturated fatty acids found in vegetable oils. Palmitoleic acid is primarily derived from fish oil. Arachidonic acid is primarily derived from animal sources. These five fatty acids comprise the major unsaturated fatty acids of commercial value. The structures of these fatty acids are shown below:
CH
3
(CH
2
)
5
CH═CH(CH
2
)
7
CO
2
H
palmitoleic
acid
CH
3
(CH
2
)
7
CH═CH(CH
2
)
7
CO
2
H
oleic acid
CH
3
(CH
2
)
4
CH═CHCH
2
CH═CH(CH
2
)
7
CO
2
H
linoleic acid
CH
3
CH
2
CH═CHCH
2
CH═CHCH
2
CH=CH(CH
2
)
7
CO
2
H
linolenic acid
CH
3
(CH
2
)
4
(CH═CHCH
2
)
4
(CH
2
)
2
CO
2
H
arachidonic
acid
The fatty acids typically occur in nature as esters, the carboxylic hydrogen being replaced by, for example, a methyl group, ethylene glycol, or glycerol.
Fish oil is a by-product of the production of fish meal. Fish oil has a triglyceride structure with a high percentage of polyunsaturated &ohgr;-3 fatty acid side chains, which contain 5-7 non-conjugated c—c double bonds. Chemical analysis indicates that fish oil is a mixture of primarily three key structures:
docosa-4,7,10,13,16,19-hexaenoic acid (DHA, 24.72%);
eicosa-5,8,11,14,17-pentaenoic acid (EPA, 31.68%) and
docosa-7,10,13,16,19-pentacnoic acid (DPA, 4.27%).
This high degree of unsaturation has prompted researchers to examine fish oil as a potential monomer for polymerization or co-polymerization. The reports that have appeared in the literature typically refer to the production of viscous oils.
Very short oligomers such as dimers and trimers have been produced from soybean oil using thermal polymerization processes, as described by R. W. Johnson, et al.,
Polymerization of Fatty Acids,
Fatty Acids in Industry 153-75 (1989). However, these processes are poorly controllable. In addition, the processes produce mainly dimers and trimers, and tend to destroy carbon-carbon double bonds.
What is needed is a process capable of polymerizing the unsaturated fatty acids in biological oils to produce useful plastic materials. Also needed is a process that can produce a high yield of product with a small catalyst load in a controlled process that minimizes the use of non-renewable, environmentally harmful materials.
SUMMARY OF THE INVENTION
The present invention provides a process for polymerizing biological oils to provide plastics from renewable resources. The invention also provides various end use products, such as molded articles, and composites, containing thermoset plastics derived from fish oil, soybean oil, and other biological oils.
To achieve the objects and in accordance with the purpose of the invention, as embodied and broadly described herein, the present invention provides methods for preparing plastics by polymerizing unsaturated fatty acid esters via Lewis-acid catalysis. The unsaturated fatty acid esters are esters of acids commonly found in biological oils, such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid or arachidonic acid. Preferably, a natural or modified soybean oil, fish oil, or other biological oil containing one or more unsaturated fatty acid esters, is used.
Methods for Lewis-acid catalyzed copolymerization of unsaturated fatty acid esters and an olefin, and including the copolymerization of two or more olefins and a biological oil, are also provided. The preferred olefin comonomers include divinylbenzene, norbornadiene and dicyclopentadiene. In a particularly preferred embodiment, a natural biological oil is modified prior to the Lewis-acid catalyzed copolymerization by one or more of a variety of suitable modification processes, including conjugation, metathesis, or cometathesis.
According to particularly preferred aspects of the invention, thermoset plastics are obtained by conjugating a natural biological oil, or by metathesizing or cometathesizing such oils with additional olefins such as norbornadiene, and copolymerizing the conjugated, metathesized or cometathesized oil with a small quantity of an additional olefin via Lewis-acid catalysis. The preferred Lewis-acid catalyst is boron trifluoride diethyl etherate. The resulting plastic materials are solid thermoset plastics suitable for a wide variety of industrial uses. Among the plastics made by the processes described herein are many plastics which are expected to be biodegradeable.
The invention provides environmentally acceptable substitutes for polyethelene, various consumer and industrial products containing biological oil thermoset plastics, and composites containing such plastics. In particular, the invention provides plastic materials for the medical, agricultural, and packaging industries, molded articles and composite materials for, such as, the marine, aerospace, automobile, and sporting goods industries, construction materials, such as engineering plastics, laminates, paints, coatings, resins and adhesives, and biocompatable materials such as surgical implants and prosthesis equipment containing plastics produced by the processes described herein.
REFERENCES:
patent: 4382136 (1983-05-01), Blount
patent: 5728917 (1998-03-01), Grubbs et al.
patent: 1570740 (1967-09-01), None
patent: 1083516 (1967-09-01), None
E. H. Pryde, “Nonfood Uses For Soybean Oil,” Chapter 21, pp. 458-481.
F.D. Gunstone,“Nonfood Uses of Vegetable Oils and Their Fatty Acids,”Industrial Uses Of Soy Oil For Tomorrow, P. 17-31 (1995).
Robert W. Johnson, “Polymerization of Fatty Acids,”Fatty Acids in Industry, pp. 153-175 (1989).
Herman Aage Enemark, “The Making of Plastics from Soybean Oil,” Iowa State College, P. 18, 19, 29, 30, (1935).
Printing Ink and Coating Technical Advisory Panels, Chicago, IL, “Preparation of New Oils and Polymers from Soybean Oil,” Richard C. Larock, Sep. 15, 1997 and Sep. 16, 1997.
Herman Aage Enemark, “The Making of Platics from Soybean Oil,” Iowa State College (1935).
Hanson Mark
Larock Richard C.
Dickstein , Shapiro, Morin & Oshinsky, LLP
Iowa State University & Research Foundation, Inc.
Wu David W.
Zalukaeva Tanya
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