Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2000-10-26
2002-03-05
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
Reexamination Certificate
active
06353082
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to processes for the preparation of highly branched functional and reactive polymers. Specifically, the present invention relates to novel highly branched functional and reactive polyesters prepared through a one-step process.
BACKGROUND OF THE INVENTION
Highly branched polymers can be made by multi-step or one step process. Multi-step generation processes were exemplified by Frechet in U.S. Pat. No. 5,041,516 and by Hult in U.S. Pat. No. 5,418,301. Both patents described that the highly branched polymers known as dendrimer or “starburst polymer” were made through a series of growth steps consisting of repeatedly reacting, isolating, and purifying.
One-step process was first conceptualized by Flory (J. Am. Chem. Soc., 74, p2718 (1952)) who demonstrated by theoretical analysis that a highly branched and soluble polymers could be formed from one-step condensation polymerization of monomer comprising the structure AB
2
, where A and B are reactive groups. In contrast to the dendrimers, the polymer formed by AB
2
, polymerization is randomly branched. Kim et al in U.S. Pat. No. 4,857,630 disclosed that hyperbranched polyphenylenes can be prepared by one-step polymerization of AB
2
-type monomers such as (3,5-dibromophenyl)boronic acid and 3,5-dihalophenyl Grignard reagents. Baker in U.S. Pat. No. 3,669,939 described that highly branched aliphatic polyesters could be prepared by one-step melt condensation polymerization of monomers having a single carboxylic acid and multiple alcohols. Hawker et al disclosed that all aromatic, highly branched polyesters can be made by melt polymerization of 3,5-bis(trimethylsiloxy)benzoyl chloride (J. Am. Chem. Soc., 113, p4583 (1991)). U.S. Pat. No. 5,196,502 discloses the use of diacetoxybenzonic acids and monoacetoxydibenzonic acids to produce wholly aromatic polyesters. U.S. Pat. Nos. 5,225,522 and 5,227,462 disclose highly branched aliphatic-aromatic polyesters and processes for making the same. U.S. Pat. No. 5,418,301 discloses a process for preparing dendritic macromolecules. U.S. Pat. No. 5,514,764 discloses preparation of hyperbranched polyester by a one-step process of polymerizing a monomer of the formula A-R-B
2
. U.S. Pat. No. 5,567,795 discloses synthesis of highly branched polymers in a single processing step by using branching aromatic monomers and an end-capping monomer. U.S. Pat. No. 5,663,247 disclosed a hyperbranched macromolecule of polyester type comprising a central monomeric or polymeric epoxide group containing nucleus and at least one generation of a branching chain extender having at least three reactive sites of which at least one is a hydroxyl or hydroxyalkyl substituted hrodroxyl group and at least one is a carboxyl or terminal epoxide group and the process for making the same.
Most AB
2
type monomers, however, are not commercially available, and access to such monomers accordingly involves synthetic efforts, which is potentially problematic, especially on a large scale. To cope with such problem, an A
2
+B
3
approach to hyperbranched polymers has been recently revisited. In A
2
+B
3
polymerization, di- and tri-functional monomers are reacted together. For ideal A
2
+B
3
polymerization, intramolecular cyclization must be minimized as a competing and chain terminating process during polymer propagation, all A groups and all B groups should have near equal reactivity in both the monomers as well as the growing polymers, and the A and B groups should have exclusive reactivity with each other. In view of such requirements, relatively few specific combinations of A
2
+B
3
polymerization schemes have been proposed. Jikei et al (Macromolecules, 32, 2061 (1999)), e.g., has reported synthesis of hyperbranched aromatic polyamides from aromatic diamines and trimesic acid. Emrick et al (Macromolecules, 32, 6380 (1999)) has disclosed the synthesis of hyperbranched aliphatic polyethers by means of proton-transfer polymerization of 1,2,7,8-diepoxyoctane as A
2
monomer and 1,1,1-tris(hydroxymethyl)ethane as B
3
monomer.
It is known that ring open reaction between terminal epoxides with acid chlorides, in the presence of tetrabutylammonium bromide, can form an anti-Markinovkov ester product containing a primary chloride. This reaction was applied to dicpoxides and diacid chlorides to form polyesters (Kameyama et al., Macromolecules 25, p.2307 (1992)). However, no prior art teaches the use of multiple epoxides and multiple acid chlorides to prepare highly branched polymers.
It would be desirable to provide a process for producing highly branched polyesters of high molecular weight without requiring the use of AB
2
type monomers or multi-step reactions and purification.
It would be further desirable to provide a process which results in highly branched polyesters having a multiplicity of very reactive epoxy or acid chloride groups or both on the outside surface which can be further converted to other functional groups.
SUMMARY OF THE INVENTION
In accordance with one embodiment of the invention, a polymerization process for producing highly branched polyesters is disclosed comprising reacting a multi-functional di- or higher epoxide group containing compound with a multi-functional di- or higher acid chloride group containing compound, wherein at least one of the epoxide or acid chloride group containing compounds is a tri- or higher epoxide or acid chloride group containing compound.
The invention provides a process for producing highly branched polyesters in one reaction step. The present process comprises a ring opening reaction between a reactant or reactants having multiple epoxide groups and another reactant or reactants having multiple acid chloride groups. The invention has the capability of making highly branched structures of high molecular weight and has the advantages of not requiring multi-step reactions and purification. The invention yields highly branched polyesters having a multiplicity of very reactive epoxy or acid chloride or both on the outside surface which can be further converted to other functional groups, including polymerizable groups and initiating groups, which can undergo further chain extensions.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to prepare a highly branched polyester in a single step procedure. The present process utilizes the ring opening reaction of multiple epoxide group containing compounds with multiple acid chloride group containing compounds at a sufficient temperature and for a sufficient period of time to produce a highly branched macromolecule of the polyester type. In accordance with the invention, the use of compounds having multiple reactive epoxide groups in combination with compounds having multiple acid chloride reactive groups has been found to be an especially useful path to providing highly branched polyester materials. The acid chloride groups are in general more reactive than carboxylic acid groups, and the reaction between acid chloride and epoxide groups proceeds under generally less stringent conditions than epoxides and carboxylic acid groups. Further, the acid chloride and epoxide groups can advantageously directly provide highly reactive end groups in the resulting highly branched polymers.
Compounds with multiple reactive epoxide groups which may be used in the process of the invention can be represented by the following formula (I):
and compounds with multiple reactive acid chloride groups which may be used in the process of the invention can be represented by the following formula (II):
where R
1
and R
2
are each independently a monomeric, oligomeric, or polymeric compound nucleus, and n and m are integers between 2 and 100, preferably between 2 and 20, without n and m being 2 at the same time. Each R
1
and R
2
compound nucleus may comprise, e.g., a straight or branched alkyl, cycloalkyl, aryl or alkylaryl moiety, or an oligomeric or polymeric chain.
In specific embodiments, the multifunctional epoxide group containing compound may be selected from glyci
Anderson Andrew J.
Boykin Terressa M.
Eastman Kodak Company
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