Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-04-27
2004-08-17
Buttner, David J. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S300000, C524S394000, C524S397000, C524S400000, C525S330200
Reexamination Certificate
active
06777472
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to melt-processable, highly-neutralized ethylene, C
3
to C
8
&agr;,&bgr; ethylenically unsaturated carboxylic acid copolymers and process for making them. It relates to such copolymers, neutralized to greater than 90%, particularly to those neutralized to nearly to or to 100%. These copolymers are made by incorporating a sufficient amount of specific organic acid (or salt) into the copolymer before neutralization to the high level. These copolymers are useful in making molded products such as golf ball components, thermoplastic shoe soles for cleated footwear, and resilient foams for sporting goods.
DESCRIPTION OF RELATED ART
Ionomers of acid copolymers of alpha olefins, particularly ethylene, and C
3-8
&agr;,&bgr; ethylenically unsaturated carboxylic acid, have been known for a long time. U.S. Pat. No. 3,264,272 (Rees) teaches methods for making such inonomers from “direct” acid copolymers. “Direct” copolymers are polymers polymerized by adding all monomers simultaneously, as distinct from a graft copolymer, where another monomer is grafted onto an existing polymer, often by a subsequent free radical reaction. A process for preparing the acid coploymer on which the ionomers are based is described in U.S. Pat. No. 4,351,931.
The acid copolymers may contain a third softening monomer such as an alkyl acrylate or methacrylate. The ethylene acid copolymers can be described as an E/X/Y copolymers where E is ethylene, X is the &agr;,&bgr; ethylenically unsaturated carboxylic acid, particularly acylic and methacrylic acid, and Y is a softening comonomer such as a C
1
TO C
8
alkyl acrylate or methacrylate ester. X and Y can be pent in a wide range of percentages, X typically up to about 35 weight percent (wt. %) of the polymer and Y typically up to about 50 weight percent of the polymer.
The wide range of neutralization of the acid moiety in the acid copolymer by a wide range of cations is known. Typical cations include lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum, and combinations of such cations. Neutralization to 90% and higher, including up to 100%, is known, but there remains a need to achieve such a high degree of neutralization without loss of melt-processability or properties such as elongation and toughness. This is particularly so for copolymers with high acid levels and when using cations other than barium, lead and tin to neutralize the copolymer.
SUMMARY OF THE INVENTION
It has been found that, by modifying an acid copolymer or ionomer with a sufficient amount of specific organic acids (or salts thereof); it is possible to highly neutralize the acid copolymer without losing processability or properties such as elongation and toughness. The organic acids employed in the present invention are aliphatic, mono-functional, saturated or unsaturated organic acids, particularly those having fewer than 36 carbon atoms.
The thermoplastic composition of this invention consists essentially of (a) aliphatic, mono-functional organic acid(s) having fewer than 36 carbon atoms; and (b) ethylene, C
3
to C
8
&agr;,&bgr; ethylenically unsaturated carboxylic acid copolymer(s) and ionomer(s) thereof, wherein greater than 90%, preferably near 100%, and more preferably 100% of all the acid of (a) and (b) are neutralized.
With the addition of sufficient organic acid, greater than 90%, nearly 100%, and preferably 100% of the acid moieties in the acid copolymer from which the ionomer is made can be neutralized without losing the processability and properties of elongation and toughness.
The melt-processable, highly-neutralized acid copolyrner ionomer can be produced by
(a) melt-blending ethylene a,d ethylenically unsaturated C
3-8
carboxylic acid copolymer(s) or ionomer(s) thereof that are not neutralized to the level that they have become intractable (not melt-processable) with one or more aliphatic, mono-functional, saturated or unsaturated organic acids having fewer than 36 carbon atoms or salts of the organic acids, and then
(b) Adding a sufficient amount of a cation source to increase the level of neutralization all the acid moieties (including those in the acid copolymer and in the organic acid) to greater than 90%, preferably near 100%, more preferably to 100%.
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Chen John Chu
Statz Robert Joseph
Buttner David J.
E. I. du Pont de Nemours and Company
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