Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2002-06-05
2003-11-11
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S078000, C524S173000, C524S366000, C524S556000
Reexamination Certificate
active
06646033
ABSTRACT:
FIELD OF THE INVENTION
This invention describes the synthesis of new bio-based monomers and the subsequent polymers that are capable of being used in the pressure sensitive adhesive (PSA) industry. The novelty in these materials is that the starting material is derived from plant oils such as high oleic soybean oil, olive oil and other oils that are capable of being chemically functionalized. In addition, this system is an odorless and organic solvent-free novel waterborne latex or emulsion based composition, which contains internally plasticizing and cross-linkable monomers. The monomer and polymer disclosed comprise a new composition of matter and a new use for known and future genetically modified plant oils.
BACKGROUND OF THE INVENTION
Pressure sensitive adhesives (PSA) are comprised of, but not limited to, polymers, tackifiers, plasticizers and stabilizers. In the past, the polymer was derived from natural rubber. Due to the difficulty in processing this material and its limited material properties, the industry shifted towards using petroleum-based long chain aliphatic monomers and polymers. Examples of the prior art polymers include, but are not limited to butyl acrylate, 2-ethylhexyl acrylate, iso-octyl acrylate and Styrene-Butadiene Rubber (SBR). These can be synthesized into polymers using emulsion, solvent, and bulk polymerization. It is ecologically advantageous for the industry to move towards aqueous emulsion based polymerizations because of the organic solvents that are required for the solution polymerization.
Replacing some, or all, of these petroleum derived raw materials with renewable plant-based raw materials is attractive, both economically and socially, as such raw materials are cheaper and their use contributes to global sustainability by not depleting scarce resources. The use of plant and animal-based raw materials such as plant oils and lard fat is further useful as such naturally occurring compounds are usually consumed readily by microorganisms. In fact, plant triglycerides are readily hydrolyzed in vivo by lipase secreting bacterial. This could make polymers derived from such raw materials easily biodegradable in natural media. This aspect of these monomers and polymers is an additional advantage over polymers derived solely from petroleum based raw materials, very few of which are degradable by naturally occurring bacteria.
The polymer in a PSA is a viscoelastic material that is permanently as well as aggressively tacky and has enough cohesive strength and elasticity to be cleanly removed from a substrate surface. These polymer systems are typically linear, or thermoplastic, and are polymers with a slight degree of cross-linking and branching. The degree of cross-linking dictates the shear and cohesive, strength of the polymer. Petroleum based polymers, as mentioned above, are typically aliphatic chains with exactly one vinyl functional group in the monomer that participates in free radical polymerization reactions. This leads to a predominately linear polymer. In order to add a controllable degree of cross-linking and branching, a multi-functional co-monomer must be added to the system to participate in the polymerization reaction.
Monomers derived from plant oils possess an inherent degree of unsaturation that varies from plant to plant. It is well known that oils from different plants such as, but not limited to, cotton, sunflower, corn, soy bean, and linseed have different amounts of carbon-carbon double bond unsaturation. The epoxidation of this unsaturation is well known. Hydrogen peroxide oxidation of triglycerides to epoxidized triglycerides has been described by R. Oda in Journal Society of Chemical Industry Japan, 41, 195-195 (1938) and by Y. Isii, in Journal Society of Chemical Industry, Japan, 43, 255-7, 315-7, 374-9 (1940), and by Swern and Billen in Journal of Organic Chemistry, 67, 1786 (1945). Ring opening reactions of epoxidized molecules are also well known. The use of diamines, anhydrides, dicarboxylic acids, and diols has been reported in literature. One of ordinary skill in the art would know that a nucleophilic species, such as those listed above, as well as an ethylenically substituted carboxylic acid, could open an oxirane structure. These reactions are relatively easy when the epoxy ring that is undergoing the reaction is in the terminal position, that is, at the end of the molecule. In epoxidized plant oils, however, the epoxy group is necessarily internal, such that is substituted on both sides by bulky akyl groups, rendering it far less reactive towards the traditional ring opening reactants. The monomers described in this disclosure use the epoxy functional group of these plant oils with an ethylenically substituted carboxylic acid, such as, but no limited to, acrylic acid. In this disclosure, the variation of unsaturation among the various plant oils, and hence the fatty acids, is used to an advantage. Depending on the property desired in the final product, various oils, or mixtures thereof, may be used in functionalization reactions to control the structural architecture of the new bio-based polymer and control its properties over a broad range of desired material response.
In the past, triglycerides and their fatty acid derivatives have been used in several different fields, including, but not limited to, inks, coatings, molding compounds, thermosetting polymers and composites. There are literature references that disclose derivatives of fatty compounds suitable in the formation of coatings. Acryloxymethyl substituted fatty compounds have been claimed to be useful in radiation curable coating formulations and as binders in ink. Acrylate esters of castor oil have been reported to have application as binders in coatings. Ethylenically unsaturated esters of long chain alkenols have been reported to have potential use as waterborne coatings, pressure sensitive adhesives, and inks. There are numerous literature references that address the use of fatty acids and fatty acid amides as components in mold releasing agents. Also, plant oil derivatives have been used to form rigid thermosetting polymer that can be used in composite applications.
However, none of these references discussed above disclose the use of plant oil derivatives, such as fatty acid esters, for the formation of pressure sensitive adhesive formulations. In addition, none of the references discussed above utilizes inexpensive and easily synthesized acrylate monomers to form latex or emulsion compositions.
The following references are disclosed as background art:
U.S. Pat. No. 4,626,582 discloses acyloxymethyl fatty compounds, which are useful as monomers in the preparation of radiation curable coatings.
U.S. Pat. No. 6,001,913 discloses latex compositions containing ethylenically unsaturated esters of long-chain alkenols which are useful as coatings, pressure sensitive adhesives, and inks.
Indian Pat. No. 153,599 describes a process for preparing novel vinyl monomers from ricinoleic acid and mixed fatty acids of castor oil.
Indian Pat. No. 154,467 describes a process for the preparation of novel acrylic monomers and polymer from castor oil and methyl ricinoleate.
U.S. Pat. No 6,121,398: High Modulus Polymers and Composites from Plant Oils.
SUMMARY OF THE INVENTION
It is an object of this invention to provide novel compositions having low organic solvents and low odor that are suitable for forming pressure sensitive adhesives. It is also an object of this invention to provide chemistries for the synthesis of monomers that can be used to form thermoplastic or thermosetting polymers, or a mixture thereof. An additional object of this invention is to provide a process for the synthesis of the novel latex or emulsion compositions. The compositions of the present invention have no precedence in the prior art.
DETAILED DESCRIPTION OF THE INVENTION
The object of this invention is to present monomers and their subsequent polymers that are derived mostly from plant and animal oil derivatives that are formulated for the use in pressure sensitive adhesives. The monom
Bunker Shana P.
Wool Richard P.
Connolly Bove & Lodge & Hutz LLP
Sanders Kriellion A.
The University of Delaware
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