Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-02-07
2002-09-03
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S305000, C525S306000, C525S309000, C525S314000, C525S071000, C525S051000, C525S057000, C525S058000, C525S060000, C525S437000
Reexamination Certificate
active
06444758
ABSTRACT:
The present invention relates to novel asymmetric hyperbranched copolymers, a process for their preparation, and to their use as polymer additives that migrate to the surface of a polymer and have beneficial effects on the surface properties of the polymer.
Random hyperbranched polymers are known. Hyperbranched polymers are obtained from the random polymerization of monomers in the presence of at least one polyfunctional monomer capable of introducing branching. Such a synthetic scheme is shown by Hawker and Devonport in “Step-Growth Polymers for High-Performance Materials: New Synthetic Methods,” Hedrick, J. L. and Labadie, J. W., Eds., Am. Chem. Soc., Washington, D.C., 1996, pp. 191-193. Hult, et al., in“Advances in Polymer Science,” Vol. 143 (1999), Roovers, J., Ed., Springer, New York, pp. 1-34, present a review of hyperbranched polymers.
U.S. Pat. No. 3,441,953 teaches that discrete esters of certain hindered dihydroxycarboxylic acids possess desirable properties and which may be used as textile softeners, lubricants, wetting and rewetting agents and textile assistants and which impart properties such as improved softness, scorch resistance, wettability and rewettability, static control, lubricity, tensile and tear strengths and sewability to textile materials. An example is given where polyethylene glycol (PEG) is reacted with dimethylolpropionic acid (2,2-bis (hydroxymethyl)propionic acid or BMPA) to form a PEG monoester of BMPA. This diol-ester is subsequently reacted with a tallow fatty acid to form the tallow fatty acid diester. In fact, it is believed that in the first step that a discrete PEG-BMPA monoester is not formed but that some hyperbranching must have occurred, resulting in a hyperbranched polyester.
Functionalization or end-capping of hyperbranched polymers with various groups is known.
WO97/23538 and WO97/23539 disclose highly branched epoxide functional and alkenyl functional polyesters respectively. The polyester is prepared by self-condensing a di, tri, or polyhydroxy functional monocarboxylic acid monomer and which polyester contains at least one carboxyl group and multi hydroxyl groups. The polyester is reacted with an epoxide containing compound such as epichlorohydrin or a compound containing an oxidizable unsaturation to introduce the epoxide functionality. Likewise, it is reacted with a compound containing allylic or acrylic groups to introduce the alkenyl functionality.
U.S. Pat. No. 3,669,939 discloses highly branched self-condensates of polyhydroxymonocarboxylic acids, for example dimethylolpropionic acid. Monocarboxylic acids may be present in the condensation reaction. The resulting resins are useful in coating compositions.
U.S. Pat. No. 5,136,014 discloses hyperbranched polyester polymers and copolymers that may be chemically capped, crosslinked, or copolymerized with diols or dicarboxylic acids. Suitable capping agents include anhydrides, acyl chlorides, isocyanates and benzylisothiocyanate.
Schmaljohann, et al., Polymeric Materials Science and Engineering, 77 (1997), p. 173, discloses that hyperbranched aromatic polyesters and a hyperbranched polyester based on self-condensation of 2,2-bis(hydroxymethyl)propionic acid may be functionalized with alkyl acid chlorides of 2 to 18 carbon atoms, resulting in hyperbranched polyesters with an amphiphilic character.
Highly branched dendritic polymers are well known, as discussed for example in “Polymeric Materials Encyclopedia,” Vol. 5 (1996), J.C. Salamone, Ed., CRC Press, New York, pp. 3049-3053. Dendritic polymers have a non-linear architecture and are intrinsically globular in shape. Discrete, stepwise synthetic methods are used to prepare highly branched pure compounds, or dendrimers. As discussed by Hawker and Devonport in “Step-Growth Polymers for High-Performance Materials: New Synthetic Methods,” Hedrick, J. L. and Labadie, J. W., Eds., Am. Chem. Soc., Washington, D.C., 1996, pp. 186-196, if the macromolecule has highly regular branching which follows a strict geometric pattern, it is a dendrimer. Dendrimers are typically monodisperse and are prepared in a multi-step approach with purifications at each stage.
The architecture of dendrimers is also discussed by Roovers and Comanita in “Advances in Polymer Science,” Vol. 142 (1999), Roovers, J., Ed., Springer, New York, pp. 179-228. Dendrimers consist of a core molecule which defines the center of symmetry of the molecule, and branching layers. Tomalia, et al., in
Angew. Chem. Int. Ed. Eng.,
29 (1990), 138-175 disclose “starburst” dendrimers which consist of an initiator core and branching groups.
Hyperbranched macromolecules result if the branching is random and irregular and are therefore not monodisperse. There are significant amounts of failure sequences present in such hyperbranched macromolecules. As discussed by Malmstroem, et al., in
Macromolecules,
28 (1995), 1698-1703, a hyperbranched material contains a mixture of linear and fully branched A repeating units and has a degree of branching of less than unity. An ideal dendritic substance has a degree of branching of unity.
It is taught in WO 99/00439 and WO 99/00440 that dendrimers are highly symmetric, while similar macromolecules designated as hyperbranched and/or dendritic may to a certain degree hold an asymmetry, yet maintaining the highly branched tree-like structure.
U.S. Pat. No. 5,418,301 teaches polyester-based dendritic macromolecules and their use as an alternative to conventional polyester alkyd resins. The dendritic macromolecules are built from a symmetric central initiator molecule or initiator polymer and a monomeric chain extender having one carboxyl and two hydroxyl groups and is optionally capped with a chain stopper. The macromolecules described therein are prepared in a stepwise fashion. The exemplified central initiator molecules are ditrimethylolpropane, trimethylolpropane and ethoxylated pentaerythritol. It is taught that the central initiator compound may be an alkoxylate polymer such as polyethylene glycol or polypropylene glycol as well as polytetrahydrofuran.
U.S. Pat. No. 5,663,247 discloses dendritic or near dendritic hyperbranched polyester-based macromolecules that comprise a central nucleus, a monomeric or polymeric chain extender with at least three reactive sites and optionally a chain stopper. The central nucleus is an epoxide compound with at least one reactive epoxide group. The chain extender has at least one hydroxyl group and at least carboxyl or epoxy group. The chain extender may be for example dimethylolpropionic acid. The examples given employ a stepwise preparation and employ as the nucleus a bisphenol A-diglycidyl ether and triglycidyl isocyanurate.
WO 96/13558 discloses a binder composition comprised of at least one unsaturated monomer and at least one unsaturated polyester. The unsaturated polyester is a dendritic or hyperbranched macromolecule comprising a nucleus, a chain extender, and a chain stopper. The nucleus has at least one reactive hydroxyl or epoxide group. The chain extender has at least two reactive hydroxyl groups and at least one reactive carboxyl group. The unsaturation in the polyester is introduced through the chain stopper. Stepwise methods are disclosed for the preparation of the polyesters. The exemplified polyesters are prepared from a nucleus of ethoxylated pentaerythritol.
WO 96/19537 discloses thermosetting materials such as composites with increased toughness with the incorporation of functionalized polyester dendritic or hyperbranched macromolecules in the thermosetting resin. The polyester macromolecules contain at least one primary or secondary reactive site. The macromolecules are built from a nucleus having at least one reactive epoxide or hydroxyl group, a chain extender with at least two reactive hydroxyl groups and at least one reactive carboxyl group and a chain stopper. The reactive sites are introduced through the chain termination. The disclosed polyesters are prepared in a stepwise fashion. The exemplified polyesters are prepared from a nucleus of pentaerythritol pentaethoxylate.
WO 97/497
Devore David
Gupta Anunay
McNamara John James
Asinovsky Olga
Ciba Specialty Chemicals Corporation
Seidleck James J.
Stevenson Tyler A.
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