Semi-telechelic nitrogen-functional oligomer

Details Semi-telechelic nitrogen-functional oligomer Semi-telechelic nitrogen-functional oligomer

2001-06-21

2002-09-17

Pezzuto, Helen L. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S258000, C526S260000, C526S266000, C526S303100, C526S317100, C526S318400, C526S320000, C526S321000

Reexamination Certificate

active

06451951

ABSTRACT:

The present invention relates to an oligomer including a nitrogen functionality and at least one ethylenic unsaturation. In particular, this oligomer has a nitrogen-functionality at one end of the oligomer, referred to herein as a semi-telechelic nitrogen-functionality, and at least one ethylenic unsaturation pendant to the oligomer backbone. Further, this invention relates to methods of preparing the oligomer.
U.S. Pat. No. 3,914,165 to Gaske discloses radiation curable amine containing monomers based on multifunctional acrylates which are partially functionalized with diethyl amine. Gaske discloses that these monomers are useful as amine synergists which are oxygen scavengers used to overcome the inhibiting effects of oxygen on the cure rate of radiation curable materials. Gaske exemplifies the use of these monomers in coatings such as pigmented inks and showed that formulations containing these monomers readily cured in the presence of oxygen. In “
Chemistry
&
Technology of UV
&
EB Formulation for Coatings, Inks
&
Paints”,
Volume II, edited by G. Webster, John Wiley & Sons, Ltd., New York, N.Y., it is also disclosed that amine acrylates such as the monomers of Gaske may promote pigment wetting. However, one deficiency with the nitrogen-functional monomers of Gaske is that in the process to prepare these monomers, the addition of the amines to the multifunctional acrylates is a random process which leads to a mixture of monomers including monomers with more than one amine functionality and monomers without an amine functionality.
In the present invention, a new class of nitrogen-functional, ethylenically unsaturated oligomers is provided which are useful as polymerizable dispersants and for radiation curable formulations. In particular, the oligomers of this invention have a single nitrogen-functionality located at one end of the oligomer chain. The semi-telechelic nitrogen-functionality is believed to allow the nitrogen-functionality to absorb onto the pigment surface without steric hindrance with the pendant polymerizable groups. Further, the oligomer chain containing the pendant ethylenic unsaturations may project away from the pigment surface into the hydrophobic monomers of the medium. These ethylenic unsaturations pendant to the oligomer backbone are unencumbered by the nitrogen-functionality and may readily react with the other monomers in the medium. Further, the method of preparing the semi-telechelic nitrogen-functional oligomers yields oligomers with a single nitrogen-functionality on each oligomer chain.
The first aspect of this invention provides a semi-telechelic nitrogen-functional oligomer with formula:
R
1
R
2
N—(CH
2
)
m
—(NH)
n
—A
where A is the residue of a macromonomer bearing at least one pendant ethylenic unsaturation and where A has a degree of polymerization in the range of 2 to 50, where n is 0 or 1, where m is 0 when n is 0, where m is an integer in the range of 0 to 18 when n is 1, and where R
1
and R
2
are groups independently selected from the group consisting of H, C
1
to C
12
branched, unbranched, and cyclic alkyl; phenyl; and substituted phenyl subject to the limitation that only R
1
or R
2
is H; or where R
1
R
2
N— is a cyclic group.
The second aspect of this invention provides a method of preparing a semi-telechelic nitrogen-functional oligomer with formula:
R
1
R
2
N—(CH
2
)
m
—(NH)
n
—A
where A is the residue of an macromonomer bearing at least one pendant ethylenic unsaturation and has a degree of polymerization in the range of 2 to 50, where n is 0 or 1, where m is 0 when n is 0, where m is an integer in the range of 0 to 18 when n is 1, and where R
1
and R
2
are groups independently selected from the group consisting of H, C
1
to C
12
branched, unbranched, and cyclic alkyl; phenyl; and substituted phenyl subject to the limitation that only R
1
or R
2
is H, or where R
1
R
2
N— is a cyclic group; including the steps of preparing a terminally unsaturated precursor macromonomer bearing pendant functional groups, reacting an amine with the terminal unsaturation of the terminally unsaturated precursor macromonomer, and reacting modifiers comprising ethylenic unsaturation with the pendant functional groups.
As used herein, the term “(meth)acrylate” denotes both “acrylate” and “methacrylate”, the term “(meth)acrylic” denotes both “acrylic” and “methacrylic”, and the term “(meth)acrylamide” denotes both “acrylamide” and “methacrylamide”.
As used herein, the term “pendant” means that a group, a functional group, or a reactive moiety, is not in the backbone structure of a macromonomer or an oligomer. Further, the reaction of a pendant group for the present invention will not cause any changes of the backbone structure of the macromonomer or oligomer.
The semi-telechelic nitrogen-functional oligomer of this invention is an oligomer with at least one ethylenic unsaturation pendant to the oligomer backbone and with one end of the oligomer terminated by a nitrogen containing group. The ethylenic unsaturation pendant to the oligomer provides a means to incorporate the oligomer into a polymer matrix. The nitrogen functionality provides a functional group which may bond or associate with the surface of a pigment and aid in the dispersion of a pigment. The oligomer of this invention may be represented by formula (I):
R
1
R
2
N—(CH
2
)
m
—(NH)
n
—A.  (I)
in which A is the residue of a macromonomer with at least one pendant ethylenic unsaturation and the component R
1
R
2
N—(CH
2
)
m
—(NH)
n
represents the nitrogen functionality.
The semi-telechelic nitrogen-functional oligomer may be prepared by a general scheme which is summarized below. This general scheme is used to illustrate the invention only. It is not intended to limit the scope of the invention which is defined herein by the specification and the claims. It is also contemplated that some of the steps may be carried out simultaneously or sequentially.
1) Preparation of a terminally unsaturated precursor macromonomer which includes functional groups.
2) Addition of nitrogen functionality to the terminal unsaturation of the precursor macromonomer.
3) Reaction of the functional groups with modifiers including ethylenic unsaturation.
The semi-telechelic nitrogen-functional oligomer may be prepared by first preparing a terminally unsaturated precursor macromonomer, referred to herein as “precursor macromonomer”. The precursor macromonomer includes as polymerized groups the residues of at least one first monomer and at least one second monomer which includes a functional group. The precursor macromonomer is characterized as having an ethylenic unsaturation at one end. The terminal unsaturation may be connected directly to an end monomer residue or may be connected to a linker group, as described herein in formulas (IV) and (V), which is connected to an end monomer residue. In one embodiment, the precursor macromonomer may be represented by the formula (II):
Q—[Y]
y
[T]
z
—H  (II)
in which Y is the residue of at least one first monomer and T is the residue of at least one second monomer. The individual residues Y and T may be arranged to form alternating, random, or block structures in the precursor macromonomer. The group Q is the terminal unsaturation and optionally, includes a linker group.
The first monomer is an ethylenically unsaturated monomer and may be selected from the group consisting of olefins, styrenes, substituted styrenes, vinyl esters, vinyl ethers, (meth)acrylic acid, alkyl esters of (meth)acrylic acid, hydroxyalkyl esters of (meth)acrylic acid, (meth)acrylamide, N-substituted (meth)acrylamides, methyl vinyl ketone, and mixtures thereof. Preferred monomers include monomers with an &agr;,&bgr;-unsaturated carbonyl group such as alkyl esters of (meth)acrylic acid.
Examples of functional groups include halide, hydroxy, hydroxyalkyl, hydroxyaryl, esters of carboxylic acids, aldehyde, ketone, alkylsiloxy, alkoxysilyl, arylsiloxy groups. Suitable second monomers include allyl alcohol, allyl esters such as allyl acetate, vinyl chlorid

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