Polymers derived from low unsaturation polyamines

Details Polymers derived from low unsaturation polyamines Polymers derived from low unsaturation polyamines

2001-05-25

2003-10-21

Hampton-Hightower, P. (Department: 1711)

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

Synthetic resins

From carboxylic acid or derivative thereof

C528S044000, C528S061000, C528S064000, C528S068000, C528S076000, C528S078000, C528S085000, C528S328000, C528S407000, C521S159000, C524S710000, C524S840000, C525S420000, C525S440030, C525S459000

Reexamination Certificate

active

06635737

ABSTRACT:

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
TECHNICAL FIELD
The invention relates to polymers and, in particular, polymers wherein at least one of the monomers is a polyamine with end group unsaturation no greater than 0.006 milliequivalents per gram.
BACKGROUND OF THE INVENTION
Relatively low unsaturation, high molecular-weigh polyols are known and have unsaturation of about 0.02 to 0.06 milliequivalents per gram (meq/g). Low unsaturation means that the ends of the polyol, of which there must be two or more, contain a very high proportion of —OH (alcohol) groups, with very few of the ends containing —CH═CH
2
groups, the latter being known as “unsaturated.”
U.S. Pat. No. 5,100,997 ('997 patent) discloses the preparation of elastomers using high molecular weight polyols and polyamines having low unsaturation. The polyols were prepared using a double metal cyanide (DMC) complex catalyst and had end group unsaturation of no greater than 0.06 meq/g of polyol. DMC catalysts can yield polyols that have unsaturation that is largely independent of the molecular weight of the polyol. The polyamines were produced by amination of the polyols in about 85% conversion, with the remainder being unconverted alcohol groups. The polyols were reacted with isocyanates to produce polyurethanes. On the other hand, when the polyamines were reacted with isocyanates, they produced polyureas. U.S. Pat. No. 5,096,993 discloses that elastomer properties are improved when the degree of unsaturation is reduced to less than 0.04 and 0.02 meq/g, respectively, of these polyols. U.S. Pat. No. 5,185,420 discloses two samples of a polyol having unsaturation of 0.005 and 0.007 meq/g that were subsequently reacted with a diphenylmethane diisocyanate to form a polyurethane.
More recently low unsaturation, high molecular-weight polyols having a degree of unsaturation no greater than 0.006 meq/g were produced and have been commercialized under the trade name Acclaim®. The catalysts used to create the Acclaim® polyols are a new class of DMC catalysts known as the Impact® catalysts. U.S. Pat. No. 5,627,120 ('120 patent) describes some of the high molecular-weight polyols produced by Impact® catalysts. The advantages of Acclaim® polyol technology over conventional polyol technology are well known. Some of the advantages lie in the physical properties of polyurethanes that are produced by reacting these low unsaturation Acclaim® polyols with polyisocyanates.
It is also well known that conventional alcohols can be converted into amines. One of many methods for this transformation includes the cyanoethylation of alcohols, followed by reduction of the cyano group with hydrogen to provide aminoethyl ethers. Other exemplary conversions of polyols to amine-terminated polyethers are described in U.S. Pat. No. 3,654,370 and U.S. Pat. No. 4,766,245. U.S. Pat. No. 4,902,777 discloses an amine produced from a polyol having an unsaturation of 0.009 meq/g.
Conventional polyamines have been used to make epoxy polymers and polyureas. Such conventional polyamines are exemplified by amine-terminated polyethers, such as those produced by the Huntsman Corporation (Huntsman) under the trade-name of Jeffamines. Comparable products are made by the BASF Corporation (BASF). These polyamines are combined with epoxy-rich monomers and polymers or with polyisocyanates to create epoxy polymers and polyureas, respectively. The polyisocyanates are either monomers with more than one isocyanate or pre-polymers with more than one isocyanate, and these may have a plurality of bond types forming the backbone of the pre-polymers. Both Huntsman and BASF utilize conventional polyols with unsaturation that is greater than 0.01 milli-equivalents/gram, and generally greater than 0.03 milli-equivalents/gram, to create their commercial polyamine products. These amine-containing products carry forward the unsaturation level of the polyol raw materials. U.S. Pat. No. 6,077,926 describes some physical property improvements in polyurethane elastomers that are derived from having low unsaturation, defined as 0.04-0.07 meq/g of unsaturation, in comparison to polyols with unsaturation of generally 0.10 meq/g or greater. U.S. Pat. No. 4,902,768 discloses elastomers and processes for their production from polyamines.
SUMMARY OF THE INVENTION
An object of the present invention is, therefore, to provide polymers derived from low unsaturation polyamines that are derived from low unsaturation polyols, where “low” is defined as less than or equal to 0.006 milli-equivalents per gram.
Another object of this invention is to provide such low unsaturation polyamine-derived polymers, having superior physical properties.
Although the '997 patent mentions low unsaturation polyamines made from relatively-low unsaturation, high molecular-weight polyols having end group saturation of less than 0.06 meq/g, the '997 patent does not, however, teach any advantage for using products made from low unsaturation polyamines. The implication is that experiments concerning the physical properties of low unsaturation polyamines may not have been performed, or if so, the results were insufficiently interesting for the inventors of the '997 patent to disclose any physical property advantages. Similarly, the '120 patent does not suggest the production or advantages of low unsaturation high molecular weight (LUSHMW) polyamines or of products made from them.
The present invention provides polymers, including and exemplified by, but not limited to polyureas, made with LUSHMW polyamines made from low unsaturation, high molecular weight polyols, such as Acclaim®-derived polyols. Polymers derived from amine-functionalized LUSHMW polyamines (LUSHMW-AF polymers) have surprisingly superior properties to those of polymers made with commercially available polyetheramines.
An advantage of this invention is that polymers, and more particularly polymers derived from amine-functionalized polyethers (LUSHMW-AF polyethers), made from the LUSHMW polyols (<0.006 meq/g unsaturation) are stronger and tougher than polymers made with conventional polyamines. Stronger and tougher polymers last longer and are useful under more aggressive conditions in service than polymers made with conventional technology.
Another advantage of this invention is that stronger and tougher polymers may permit equal service lifetime with smaller parts or thinner coatings than those required with conventional technology.
The final physical and mechanical properties of these product polymers may be dictated by the combination of the properties of the starting chemicals. The better the properties of polyols and/or polyamines, the better the properties of the final products. The physical and mechanical properties of the resulting polymers improve as molecular weight increases, an effect of having more chain extension and fewer chain termination events. Thus, one explanation for some of the advantages of the LUSHMW-AF polymers is that higher molecular weight polymers are formed when the individual chains contain two —OH or two amine groups, rather than when individual chains contain unsaturated end groups. Unsaturation leads to polymer chain termination events, and thus molecular weight limitation of the final polymer.
Similarly, Acclaim®-derived triamines (with theoretically three amine groups per molecule) have a much lower unsaturation than conventional triamines, and thus the properties that would be obtained from a perfect triamine, and those of the LUSHMW-AF polymers made from them, are much more closely approximated by an Acclaim®-derived triamine than a conventional triamine.
Additional objects and advantages of this invention will be apparent from the following detailed description of preferred embodiments thereof.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In a preferred embodiment of the present invention, low unsaturation high molecular weight (LUSHMW) polyols having an unsaturation level below or equal to 0.006 milli-equivalents per gram, and preferably below 0.004 meq/g, and molec

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