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
1999-12-16
2001-08-07
Cain, Edward J. (Department: 1714)
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...
C524S846000, C525S419000, C525S420000, C525S421000
Reexamination Certificate
active
06271306
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to water-borne adhesives and adhesive emulsions comprising a grafted polyolefin made by reacting a polyolefin with an amino carboxylic acid, and optionally an ethylenically unsaturated monomer having functionality capable of reacting with an amino group.
The invention further relates to a superior functionalized polybutylene which is suitable for several new application such as for hot melt adhesives and for emulsions. Applicants have discovered a new method which results in the grafting of small molecules of bi-functional N-substituted diacids to an unsaturated carboxylic acid, such as maleic anhydride, which can be grafted to polybutylene. The small chelate, iminodiacetic acid (IDA), is very effective because it is very reactive and can coordinate with most metals to form stable structures. The increased functionality of the grafted polymer provides higher adhesive strength in adhesive joints in a number of different substrates.
BACKGROUND OF THE INVENTION
Because of the unique set of properties of polyolefins such as polybutylene and polypropylene, particularly their high compliance compared to other polyolefins and their comparatively low melting temperature, a functionalized version becomes an excellent candidate to fill the requirements of a structural hot melt adhesive. Polybutylene without functional groups lacks the functionality or polarity needed for the adhesion to high surface energy substrates, a necessary characteristic for both hot melt adhesives and their constituents.
Polybutylene, like other polyolefins, has no functionality on the chain and therefore artifacts made from this polymer have very low surface free energy and can not be decorated by painting or printing. In the past, researchers have reacted functional groups on the surface of polyolefins by various means using highly oxidative techniques to induce bonding sites with reagents leaving hydroxyl or carboxyl groups. Also, melt reactions have been carried out to functionalize the bulk of the polyolefin material by a free radical initiated reaction induced by organic peroxides.
A large number of polymer companies commercially offer functionalized polyolefin materials such as acrylated and maleated polypropylene and polyethylene. Techniques used to modify these polymers provide one or, at most, two acid groups per grafting site. The present inventor has found that by increasing the number of functional groups to three or greater per grafting site one can substantially improve the polarity and hence improve the polymer's performance in several end use application.
Additionally, there is an ever increasing impetus to replace or supplement solvent-based polymer coating compositions with aqueous-based counterparts due to the environmental toxicity and flammability problems posed by the use of volatile organic solvents. However, even where aqueous-based polymer compositions have been devised, their production has usually entailed the intermediate use of organic solvents, requiring subsequent removal which is costly and time-consuming, or the incorporation of a certain amount of a solvent in the final composition which acts to ensure proper film-formation on coating (known as a coalescing solvent). There is therefore also now increasing pressure to significantly reduce or eliminate the volatile organic contents (VOCs) in aqueous-based polymer composition syntheses both as components in their production (even if subsequently removed) and in the resulting composition as an aid to film coalescence.
In the present invention, applicants have found unexpectedly that multi-carboxylic acid as the functional group can co-ordinate very effectively with most metals to form stable, e.g. octahedral, anionic complexes. For example, two moles of iminodiacetic acid contain four carboxylic acid groups, which can react with metal ions to form to have stability constant in excess of 10
10
. The introduction of carboxylic functionality into polyolefins allow for more water solubility as well as production of water borne products which are environmentally desirable.
SUMMARY OF THE INVENTION
The present invention is directed to a grafted polyolefin comprising the reaction product of: (a) a polyolefin which had been grafted with an unsaturated carboxylic acid anhydride or acid thereof; and (b) an amino carboxylic acid.
The instant invention is also directed to a grafted polyolefin comprising the reaction product of: (a) a polyolefin; and (b) an amino carboxylic acid.
The invention further relates to a grafted polyolefin comprising the reaction product of: (a) a polyolefin; (b) an unsaturated carboxylic acid anhydride or unsaturated carboxylic acid; and (c) an amino carboxylic acid.
The invention also describes a grafted polybutylene polymer comprising the free radical grafting reaction product of polybutylene and iminodiacetic acid.
In a further aspect of the invention, there is described a grafted polybutylene polymer comprising the free radical grafting reaction product of polybutylene and maleic anhydride further reacted with iminodiacetic acid.
The invention also provides (1) a compound (adduct), made by reacting maleic acid anhydride (ester) with iminodiacetic acid or a salt thereof and useful for grafting polyolefins, which compound has a formula selected from the group consisting of formula [1], [2], [3] below and mixtures thereof; (2) a process for making multi-functional polyolefins by grafting polyolefin such as polypropylene or polybutylene with such compound; and (3) a multifunctionalized polyolefin made by such process. The compound (adduct) formula selected from the group consisting of formula [1], [2], [3] below and mixtures thereof:
wherein M
+
is Na
+
, K
+
, Li
+
or Cs
+
The compound (monomer) can also further react to form dimer, trimer and oligomer.
The invention further provides a grafted polybutylene homopolymer or copolymer having 1-50, preferably 1-30, more preferably 2-15 mole percent of an alpha olefin having from 2-8 carbon atoms, wherein the polybutylene is grafted with from about 0.01 to about 30, preferably from about 1 to about 15, more preferably from about 3 to about 10 weight percent of iminodiacetic acid
The present invention also provides an adhesive composition comprising the multi-functional polyolefins, particularly multi-functional poly-1-butene, described above. Particularly, the present invention also provides an adhesive composition comprising the reaction product of (a) a polybutylene compound consisting of polybutylene modified by grafting thereto an unsaturated monomer bearing an acid, ester or acid anhydride group, with (b) an amino polycarboxylic acid compound or a salt thereof bearing at least one primary or secondary amine groups, which are reactive with the anhydride group.
The invention is also directed to an emulsion composition comprising: (1) 25 to 55 weight percent of a grafted polyolefin comprising the reaction product of (i) a polyolefin, (ii) an ethylenically unsaturated monomer having functionality capable of reacting with an amino group and (iii) an amino carboxylic acid or a salt thereof; (2) a minor amount up to 10 weight percent of a surfactant; and (3) 55 to 80 weight percent water.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
While the present invention is described in connection with preferred embodiments, it will be understood that it is not intended to limit the invention to those embodiments. On the contrary, it is intended to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
The preferred mode of grafting the polyolefins is via free-radical grafting using peroxide initiators although other initiators such as azo compounds can be used. The organic peroxides which may be suitably used in the present invention are those having a decomposition temperature of preferably from 80° C. to 230° C., preferably from 110° C. to 220°
Hwo Charles C.
Rodriguez Manuel Soler
Cain Edward J.
Shell Oil Company
Tsang Y. Grace
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