Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-02-19
2001-05-01
Woodward, Ana (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C528S229000, C528S392000, C528S422000, C528S423000, C528S492000
Reexamination Certificate
active
06225419
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to styrene grafted polyamine composition which is useful as a wood glue composition component.
BACKGROUND TO THE INVENTION
Polymers of carbon monoxide and olefins generally referred to as polyketones are well known in the art. The class of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon are of particular interest among polyketone polymers. This class of polymers is disclosed in numerous U.S. Patents assigned to Shell Oil Company, exemplified by U.S. Pat. Nos. 4,880,865 and 4,818,811 which are incorporated herein by reference. Polyketone polymers display a well balanced set of mechanical properties which make them particularly useful as engineering thermoplastics.
Other materials having useful properties have also been formed from the combination of various olefins and carbon monoxide. Among these, are relatively low molecular weight materials comprising oligomers or low molecular weight polymers. A monomer other than carbon monoxide and ethene comprises at least 20% wt of the total weight of the polymer. Two olefinic monomers are ordinarily used such as ethene and propene with a relatively low ratio of ethylene to propene (on a weight or molar basis) compared to the linear alternating aliphatic polyketones used as engineering thermoplastics. The monomeric mix will typically include about 50% mole carbon monoxide and about 50% mole of olefins with at least about 30% by weight of the total olefin content comprised of C
3
or higher olefins.
These oligomers or low molecular weight polyketones can be employed as thermosets. In such applications they are cured with a curing agent which is generally an amine. Curing may be achieved in the presence of an acid catalyst. Such resins are preferable to existing thermosets in a variety of applications due to reduced environmental nuisances, ease of use, and property mix.
One application of these thermosets is as an adhesive. More particularly, they are useful as glues for wood composites in the preparation of plywood and flake or particle board. The wood composite industry has generally used adhesives such as urea formalde-hyde resins and phenol formaldehyde resins. However, many of the wood composites prepared with them are losing favor in important market segments even though the demand remains generally high for a high impact resistant wood composite with good dimensional stability in the presence of moisture. Much of this is attributable to environmental and safety factors associated with the systems.
Pyrroles may be prepared by a Paal-Knorr reaction by heating a 1,4-dicarbonyl compound with ammonia or primary amines. An example of a Paal-Knorr type reaction may be found in WO 93/19114. In that publication an olefin-carbon monoxide polymer is reacted with an amino acid or a derivative thereof, resulting in polymeric pyrroles having carboxyl functionality or a functionality convertible thereto. It remains desirable to extend the family of polymeric pyrroles having functional groups other than the carboxyl functionality. The amine reactant in the Paal-Knorr reaction need not be a monoamine. For example, in EP-A-0,372,602 the olefin-carbon monoxide polymers are reacted with polyamines. However, these polymeric amines are cross-linked and therefore less applicable in, for example, curable resin compositions.
Use of resin compositions as binder in the preparation of glued wood products such as plywood, particle board, MDF, OSB and laminated beams is known from PCT/EP95/04324. These resin compositions comprise one or more olefin carbon monoxide polymers, optionally of different molecular weight, one or more polyamines such as hexamethylenediamine as curing agent and optionally one or more curing catalysts. They may further comprise a diluent and additional components such as viscosity modifiers, flame retardants, gap filling agents, antioxidants, UV stabilizers and colorants. As is shown in PCT/EP95/04324, these resin compositions compare favorably with curable resins based on urea- or phenolformaldehyde. While these glue systems provide good adhesion, their viscosity and pot life are not ideal for many commercial applications. Lowering their viscosity and increasing their pot life would extend the range of applications for which olefin/CO resins could be used. In particular, they could be made much more suitable for use in the production of plywood and oriented strand board under such conditions.
SUMMARY OF THE INVENTION
These and other objects are accomplished by a polymeric amine which is the product of a diamine having one of the amine groups being more reactive than the other amine group with polymer blend, the polymer blend being a product of a radical polymerization of a vinyl monomer in the presence of an polyketone. This blend includes both grafted and free vinyl polymers, with at least some of the ketone functional groups in a 1,4 configuration providing reactive sites for combination with the amines to form pyrrolediyl units. The grafted polymeric amine therefore comprises: N-substituted 2,5-pyrrolediyl groups incorporated in the backbone wherein the N-substituted 2,5-pyrrolediyl group may be represented by the general formula
wherein R independently represents a hydrogen or a hydrocarbyl group and B represents the substituent containing at least one primary amino group; and pendant monomer groups. This grafted polymeric amine is useful as a component in a wood glue composition and inclusion of the grafted vinyl polymer results in improved water resistance. In another aspect, the present invention includes a method to produce the grafted polymeric amines, and a wood glue prepared therefrom.
DESCRIPTION OF A PREFERRED EMBODIMENT
The olefin carbon monoxide polymers that are used for the preparation of the polymeric amines and vinyl grafted carbon monoxide-olefm polymers may be perfectly alternating (molar ratio olefin:carbon monoxide equals 1:1 with 1,2-addition of the olefin), semiperfectly alternating (molar ratio olefin:carbon monoxide equals 1:1, but with some olefin addition other than 1,2) or random (e.g., having a carbonyl content of about 30 up to 50 mole percent as disclosed in U.S. Pat. No. 846,406). The theoretical degree of conversion to the pyrrolediyl is limited by the distribution of the carbonyl groups as 1,4-dicarbonyl entities across the polymer chain. Preferably the olefin-carbon monoxide is perfectly alternating or semiperfectly alternating.
The olefin-carbon monoxide polymer may be prepared from ethene, styrene, substituted styrene, an olefinically unsaturated hydrocarbon such as vinyl acetate, ethyl acrylate or N-vinylpyrrolidone, an alpha-olefin, an internal olefin, or a mixture thereof. The polymer is prepared from olefins having from 2 up to 14 carbon atoms, in particular from alpha-olefins having from 2 to 8 carbon atoms. Formation of polymers of still larger olefins is possible but not preferred. More preferably, the olefin-carbon monoxide polymer is a copolymer of carbon monoxide and an olefin selected from ethene, propene and styrene. Particularly preferred are perfectly alternating polymers of ethene and carbon monoxide or styrene and carbon monoxide; perfectly or semiperfectly alternating copolymers of propene and carbon monoxide; perfectly alternating copolymers of ethene/styrene and carbon monoxide; and perfectly or semiperfectly alternating copolymers of ethene/propene and carbon monoxide or propene/styrene and carbon monoxide.
In particular when the olefin-carbon monoxide polymer is an alternating polymer of an alpha-olefin having three or more carbon atoms, the alpha-olefin may be incorporated predominantly in a regioregular fashion or in a regio-irregular fashion. Use of a regio-irregular polymer has the advantage that its viscosity is lower than that of an otherwise comparable (regio-regular) polymer.
The olefin-carbon monoxide polymer may have a molecular weight ranging from 200 to about 500,000 daltons. For a curable resin composition, the polymer suitably has a molecular weight ranging from 5
Shell Oil Company
Woodward Ana
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