Protein-containing adhesives, and manufacture and use thereof

Abstract

The invention provides protein adhesives containing certain additives and methods of making and using such adhesives. The protein adhesives contain ground plant meal or an isolated polypeptide composition obtained from plant biomass in combination with certain additives, such as an exfoliated clay or partially exfoliated clay.

What is claimed is: 
     
         1 . An adhesive composition comprising:
 (a) from about 1% to about 90% (w/w) of a reactive prepolymer;   (b) ground plant meal in an amount sufficient to disperse the reactive prepolymer in an aqueous medium; and   (c) at least one first additive selected from the group consisting of a partially exfoliated clay, an exfoliated clay, an intercalated clay, cellulose nanoparticles, and a mixture of a silicone and a terpene compound.   
     
     
         2 . The composition of  claim 1 , wherein the ground plant meal has a particle size in the range of from about 1 μm to about 200 μm. 
     
     
         3 . The composition of  claim 1 , wherein the ground plant meal has a particle size in the range of from about 10 μm to about 70 μm. 
     
     
         4 . The composition of  claim 1 , wherein the ground plant meal is present in an amount sufficient to disperse the reactive prepolymer in an aqueous medium to form a dispersion or emulsion that exhibits no phase separation by visual inspection for at least 5 minutes after mixing the reactive prepolymer with the ground plant meal. 
     
     
         5 . The composition of  claim 1 , wherein the ground plant meal is present in an amount such that the viscosity of the adhesive formulation increases by no more than about 50% within about 20 minutes after mixing the prepolymer and ground plant meal with a nucleophile. 
     
     
         6 - 7 . (canceled) 
     
     
         8 . The composition of  claim 1 , wherein the ground plant meal is present in an amount from about 5% to about 35% (w/w) of the adhesive composition. 
     
     
         9 . The composition of  claim 1 , wherein the ground plant meal is derived from corn, wheat, sunflower, cotton, rapeseed, canola, castor, soy, camelina, flax, jatropha, mallow, peanuts, algae, sugarcane begasse, tobacco, whey, or a combination thereof. 
     
     
         10 . An adhesive composition comprising:
 (a) from about 1% to about 90% (w/w) of a reactive prepolymer;   (b) from about 10% to about 98% (w/w) of an isolated polypeptide composition capable of dispersing the reactive prepolymer in an aqueous medium; and   (c) at least one first additive selected from the group consisting of a partially exfoliated clay, an exfoliated clay, an intercalated clay, cellulose nanoparticles, and a mixture of a silicone and a terpene compound.   
     
     
         11 . A two-part adhesive composition comprising:
 (a) a first part (Part A) comprising from about 5% to about 90% (w/w) of a reactive prepolymer, wherein the reactive prepolymer is a polyisocyanate-based prepolymer, an epoxy-based prepolymer, or a combination thereof;   (b) a second part (Part B) comprising from about 10% to about 99% (w/w) of an isolated polypeptide composition capable of dispersing the reactive prepolymer in an aqueous medium; and at least one first additive selected from the group consisting of a partially exfoliated clay, an exfoliated clay, an intercalated clay, cellulose nanoparticles, and a mixture of a silicone and a terpene compound.   
     
     
         12 . The composition of  claim 1 , wherein the first additive is a partially exfoliated clay. 
     
     
         13 . The composition of  claim 12 , wherein the partially exfoliated clay has a mean particle size of less than about 500 nm. 
     
     
         14 . The composition of  claim 12 , wherein the partially exfoliated clay is a partially exfoliated smectite. 
     
     
         15 . The composition of  claim 12 , wherein the partially exfoliated clay is a partially exfoliated montmorillonite. 
     
     
         16 . The composition of  claim 1 , wherein the first additive is an exfoliated clay. 
     
     
         17 . The composition of  claim 16 , wherein the exfoliated clay has a mean particle size of less than about 100 nm. 
     
     
         18 . The composition of  claim 16 , wherein the exfoliated clay is an exfoliated smectite. 
     
     
         19 . The composition of  claim 16 , wherein the exfoliated clay is exfoliated montmorillonite. 
     
     
         20 . The composition of  claim 1 , wherein the first additive is an intercalated clay. 
     
     
         21 . The composition of  claim 20 , wherein the intercalated clay is an intercalated smectite. 
     
     
         22 . The composition of  claim 20 , wherein the intercalated clay is a smectite that has been intercalated with a quaternary ammonium compound. 
     
     
         23 . The composition of  claim 20 , wherein the intercalated clay is an intercalated montmorillonite. 
     
     
         24 . The composition of  claim 20 , wherein the intercalated clay is montmorillonite intercalated with a dimethyl-di(C 14 -C 18 )alkyl ammonium salt. 
     
     
         25 . The composition of  claim 1 , wherein the first additive is a mixture of a silicone and a terpene compound. 
     
     
         26 . (canceled) 
     
     
         27 . An adhesive composition comprising:
 (a) from about 1% to about 90% (w/w) of a reactive prepolymer;   (b) ground plant meal in an amount sufficient to disperse the reactive prepolymer in an aqueous medium; and   (c) at least one first additive selected from the group consisting of a fire retardant and wood preservative.   
     
     
         28 . An adhesive composition comprising:
 (a) from about 1% to about 90% (w/w) of a reactive prepolymer;   (b) from about 10% to about 98% (w/w) of an isolated polypeptide composition capable of dispersing the reactive prepolymer in an aqueous medium; and   (c) at least one first additive selected from the group consisting of a fire retardant and wood preservative.   
     
     
         29 . A two-part adhesive composition comprising:
 (a) a first part (Part A) comprising from about 5% to about 90% (w/w) of a reactive prepolymer, wherein the reactive prepolymer is a polyisocyanate-based prepolymer, an epoxy-based prepolymer, or a combination thereof;   (b) a second part (Part B) comprising from about 10% to about 99% (w/w) of an isolated polypeptide composition capable of dispersing the reactive prepolymer in an aqueous medium; and   (c) at least one first additive selected from the group consisting of a fire retardant and wood preservative, which may be in Part A, Part B, or both Part A and Part B.   
     
     
         30 . The composition of  claim 1 , wherein the first additive is present in an amount of from about 0.1% to about 5% w/w of the adhesive composition. 
     
     
         31 . The composition of  claim 10 , wherein the isolated polypeptide composition is derived from corn, wheat, sunflower, cotton, rapeseed, canola, castor, soy, camelina, flax, jatropha, mallow, peanuts, algae, sugarcane bagasse, tobacco, whey, or a combination thereof. 
     
     
         32 - 33 . (canceled) 
     
     
         34 . The composition of  claim 10 , wherein the isolated polypeptide composition comprises one or more of the following features:
 i. an amide-I absorption band between about 1620 cm −1  and 1632 cm −1  and an amide-II band between approximately 1514 cm −1  and 1521 cm −1 , as determined by solid state Fourier Transform Infrared Spectoscopy (FTIR),   ii. a prominent 2° amide N—H stretch absorption band centered at about 3272 cm −1 , as determined by solid state FTIR,   iii. an average molecular weight of between about 600 and about 2,500 Daltons,   iv. two protonated nitrogen clusters defined by  15 N chemical shift boundaries at about 86.2 ppm and about 87.3 ppm, and  1 H chemical shift boundaries at about 7.14 ppm and 7.29 ppm for the first cluster, and  1 H chemical shift boundaries at about 6.66 ppm and 6.81 ppm for the second cluster, as determined by solution state, two-dimensional proton-nitrogen coupled NMR, and   v. is capable of dispersing an oil-in-water or water-in-oil to produce a homogeneous emulsion that is stable for least 5 minutes.   
     
     
         35 . (canceled) 
     
     
         36 . The composition of  claim 1 , further comprising a formaldehyde scavenging agent. 
     
     
         37 . The composition of  claim 36 , wherein the formaldehyde scavenging agent is H 2 NC(O)NH 2 . 
     
     
         38 . (canceled) 
     
     
         39 . The composition of  claim 1 , wherein the reactive prepolymer is a polyisocyanate-based prepolymer, an epoxy-based prepolymer, a latex-based prepolymer, a latex prepolymer, or a combination thereof. 
     
     
         40 . The composition of  claim 1 , wherein the reactive prepolymer is a polyisocyanate-based prepolymer. 
     
     
         41 . The composition of  claim 39 , wherein the polyisocyanate-based prepolymer is an organic polyisocyanate; or a reaction product between an organic polyisocyanate and a polypeptide, a polyol, an amine based polyol, an amine containing compound, a hydroxy containing compound, or a combination thereof. 
     
     
         42 . The composition of  claim 39 , wherein the polyisocyanate-based prepolymer is a polymer comprising a terminal reactive isocyanate group. 
     
     
         43 - 45 . (canceled) 
     
     
         46 . The composition of  claim 1 , wherein the reactive prepolymer is an organic polyisocyanate selected from the group consisting of polymeric diphenylmethane diisocyanate (PMDI), 4,4′-methylenediphenyl, diisocyanate (4,4′-MDI), 2,4-methylenediphenyl, diisocyanate (2,4-MDI), or a combination thereof. 
     
     
         47 . The composition of  claim 1 , further comprising water. 
     
     
         48 . The composition of  claim 47 , wherein the water is present in an amount from about 30% (w/w) to about 60% (w/w) of the adhesive composition. 
     
     
         49 - 53 . (canceled) 
     
     
         54 . The composition of  claim 1 , wherein the composition comprises a partially exfoliated clay, silicone, and a terpene compound. 
     
     
         55 . The composition of  claim 1 , wherein the composition comprises silicone, limonene, and partially exfoliated montmorillonite intercalated with a dimethyl-di(C 14 -C 18 )alkyl ammonium salt. 
     
     
         56 . A solid binder composition formed by curing a composition of  claim 1 . 
     
     
         57 . A method of bonding a first article to a second article comprising:
 (a) depositing on a surface of the first article the adhesive composition of  claim 1  thereby to create a binding area; and   (b) contacting the binding surface with a surface of the second article thereby to bond the first article to the second article.   
     
     
         58 . The method of  claim 57 , further comprising the step of, after step (b), permitting the adhesive composition to cure. 
     
     
         59 . A method of producing a composite material comprising:
 (a) combining a first article and a second article with the adhesive composition of  claim 1  to produce a mixture; and   (b) curing the mixture produced by step (a) to produce the composite material.   
     
     
         60 . The method of  claim 59 , wherein the curing comprises applying pressure, heat or both pressure and heat to the mixture. 
     
     
         61 . The method of  claim 60 , wherein the first article, the second article or both the first and second articles are lignocellulosic materials, or composite materials containing lignocellulosic material. 
     
     
         62 . (canceled) 
     
     
         63 . An article produced by the method of  claim 57 . 
     
     
         64 . An article comprising two or more components bonded together using the adhesive composition of  claim 1 . 
     
     
         65 - 66 . (canceled) 
     
     
         67 . An article produced using the adhesive composition of  claim 1 . 
     
     
         68 . The article of  claim 67 , wherein the article is a composite. 
     
     
         69 . The article of  claim 68 , wherein the composite is a random non-oriented homogeneous composite, an oriented composite, or a laminated composite 
     
     
         70 . The article of  claim 68 , wherein the composite is chip board, particle board, fiber board, oriented strand board, plywood, laminated veneer lumber, glulam, laminated whole lumber, laminated composite lumber, composite wooden I-beams, medium density fiberboard, high density fiberboard, extruded wood, or fiberglass. 
     
     
         71 - 74 . (canceled) 
     
     
         75 . An adhesive composition comprising:
 (a) from about 5% to about 40% (w/w) of a reactive prepolymer;   (b) from about 5% to about 30% (w/w) ground plant meal;   (c) from about 1% to about 40% (w/w) of a dry powder fire retardant; and   (d) from about 30% to about 70% (w/w) water.   
     
     
         76 . The adhesive composition of  claim 75 , wherein the reactive prepolymer is polymeric diphenylmethane diisocyanate. 
     
     
         77 . The adhesive composition of  claim 76 , wherein the ground plant meal is ground canola meal. 
     
     
         78 . The adhesive composition of  claim 77 , wherein the dry powder fire retardant is present in an amount ranging from 20% to about 35% (w/w) of the adhesive composition. 
     
     
         79 . The adhesive composition of  claim 78 , wherein the dry powder fire retardant is colemanite.