Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2001-07-31
2003-04-01
Hampton-Hightower, P. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S312000, C528S313000, C528S315000, C528S332000, C528S335000, C528S336000, C528S337000, C528S363000, C528S422000, C528S271000, C528S272000, C528S285000, C528S286000, C528S288000
Reexamination Certificate
active
06541600
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel highly branched polymers. Specifically, the present invention relates to water soluble and water dispersible highly branched polyamides.
BACKGROUND OF THE INVENTION
Polyamides represent one of the most important groups of polymers with excellent heat and flame resistance and high tensile strength and modulus. Branched polymers and copolymers have attracted considerable attention over the past decades, since many advanced materials with new or improved properties can be obtained therefrom. The terms “hyperbranched” and “highly branched” used herein with respect to branched polymers are intended to designate polymers having a relatively high percentage of propagated branching sites per number of polymerized monomer units, e.g. at least one branching site per every ten monomer units, preferably at least one branching site per every five monomer units and more preferably at least one branching site per every three monomer units. Highly branched polymers can be made by multi-step or one step processes. 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 monomers comprising the structure AB
2
, where A and B are reactive groups, by one-step condensation polymerization. In contrast to the dendrimers, the polymer formed by AB
2
polymerization is randomly branched. 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, one-step process for formation of a highly branched polymer may also use an A
2
+B
3
approach. 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.
With regard to the synthesis of hyperbranched polyamides from AB
2
-type monomers, Kim reported the synthesis of hyperbranched aromatic polyamides from sulfinyl amino acid chloride derivatives in organic solvents (J. Am. Chem. Soc., 114, 4947 (1992)). U.S. Pat. No. 5,514,764 disclosed preparation of hyperbranched aromatic polyesters and polyamides by a one-step process of polymerizing a monomer of the formula A—R—B
2
where R represents an aromatic moiety. U.S. Pat. No. 5,567,795 disclosed synthesis of highly branched polymers in a single processing step by using branching aromatic monomers and an end-capping monomer. With regard to A
2
+B
3
polymerization, Jikei et al (Macromolecules, 32, 2061 (1999)), e.g., has reported synthesis of hyperbranched aromatic polyamides from aromatic diamines and trimesic acid.
However, most polyamides are generally characterized by poor solubility and processability. Although aromatic polyamides with hyperbranched architecture as disclosed in Kim (J. Am. Chem. Soc., 114, 4947 (1992)) and Jikei et al (Macromolecules, 32, 2061 (1999)) cited above were found to have better solubility in several organic solvents, no prior art discloses water-soluble or water dispersible hyperbranched polyamides. Furthermore, no prior art discloses water-soluble or water dispersible hyperbranched polyamide with organic colorant being part of repeating monomeric units in polymer backbone.
It would be desirable to provide water soluble and water dispersible hyperbranched polyamides. It would be further desirable to provide such water soluble and water dispersible hyperbranched polyamides which comprise an organic colorant moiety incorporated into the polymer backbone.
SUMMARY OF THE INVENTION
In accordance with one embodiment of the invention, novel highly branched polyamide polymers are disclosed, which comprise polyamides prepared in a single step procedure of condensation polymerization of (a
1
) multi-functional di- or higher amine functional group containing monomers represented by the following formula (I) and multi-functional di- or higher carboxylic acid functional group containing monomers represented by the following formula (II), or a preformed salt of such di- or higher functional monomers, or (a
2
) multi-functional branching monomers of the formula (III):
R
1
(NH
2
)
x
(I)
R
2
(COOH)
y
(II)
A
n
—L—B
m
(III)
where in formulas (I) and (II), R
1
and R
2
are each independently a monomeric, oligomeric, or polymeric compound nucleus, x and y are integers of at least 2, preferably from 2 and 4, without x and y being 2 at the same time, and
in formula (III), one of A and B represents an amine functional group, the other of A and B represents a carboxylic acid functional group, L represents a monomeric, oligomeric, or polymeric compound nucleus linking group between A and B, n is at least 1 and m at least 2, and preferably n is 1 and m is 2 or 3;
wherein multiple monomer units of the highly branched polyamide are derived from monomers which contain an amine, phosphine, arsenine or sulfide group, such that the highly branched polyamide contains in the backbone thereof an N, P, As or S atom capable of forming an onium ion.
In a preferred embodiment of the invention, multiple monomer units of the highly branched polyamide are derived from monomers which contain a tertiary amine, phosphine, or arsenine group, such that the highly branched polyamide contains in the backbone thereof a quaternizable N, P or As atom, and most preferably a quaternizable N atom. In a particularly preferred embodiment, multiple monomer units of the highly branched polyamide are derived from tri-functional monomers of formula (I), (II) or (III) where R
1
, R
2
, or L is of the formula Q[(CH
2
)
p
]
3
wherein p represents an integer of from 1 to 6, preferably 1 to 3, and more preferably 2, and Q represents a quaternizable N, P or As atom, preferably a quaternizable N, or P atom, and most preferably a quaternizable N atom.
The present invention advantageously provides at least partially aliphatic hyperbranched polyamides which contain an onium ion forming moiety in the hyperbranched polymeric backbone, which polymers are water soluble or dispersible. The residual terminal groups of the hyperbranched polyamides may be functionalized and chemically capped, and a dye chromophore may also be incorporated into the hyperbranched polymeric backbone.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to novel highly branched polyamides prepared in a single step procedure of condensation polymerization of multifunctional monomer reactants comprising amine and carboxylic acid functional groups. Polymerization proceeds by reaction of an amine group of a first monomer unit with an acid group of a second monomer unit to form a reaction product having an amide linkage between the first and second monomer units and repetition of such amidation reaction between additional amine groups and acid groups of the multi-functional monomers and reaction products of the multi-functional monomers. In the present invention, in order to obtain a water soluble or dispersible hyperbranched polyamide, at least one of the multifunctional monomer unit reactants contains an amine, phosphine, arsenine or sulfide group, such that the highly branched polyamide contains in the backbone thereof N, P, As
Chen Huijuan D.
Wang Jin-Shan
Anderson Andrew J.
Eastman Kodak Company
Hampton-Hightower P.
LandOfFree
Water soluble and dispersible highly branched polyamides does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Water soluble and dispersible highly branched polyamides, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Water soluble and dispersible highly branched polyamides will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3085486