Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/005—Lignin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
  • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
  • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31779—Next to cellulosic
  • Y10T428/31783—Paper or wood

Definitions

• the invention is directed to adhesive compositions made of low molecular weight polyamidoamine-epihalohydrin resins (PAE resins) and certain proteins (such as soy flour or soy protein isolate) or lignin, and to their use in preparing wood composites such as laminated veneer or plywood composites.
• PAE resins low molecular weight polyamidoamine-epihalohydrin resins
• proteins such as soy flour or soy protein isolate
• lignin lignin
• PAE polymers are well-known as wet strength additives in papermaking processes. Technology for using these PAE polymers as curing agent components for protein or lignin- based adhesives is known (see US application 2005/0282988). The use of the PAE' s with proteins, such as soy flour, soy protein isolate or lignin as adhesives for lignocellulosic is known. (Kaichang Li, U.S. Patent 7,252,735, August 8, 2007)
• a current limitation of this type of adhesive is the high viscosity of the adhesive formulation at a desirable solids content and short adhesive pot life.
• the high viscosity hinders the application of the adhesive to the substrate.
• Addition of water is typically required to bring the adhesive to a workable viscosity.
• the extra water reduces the solids content, thus reducing the amount of active material added to the substrate.
• this water often must be removed for the final product at the cost of time, productivity, and energy.
• the invention is directed to compositions containing low molecular polyamidoatnine-epihalohydrins (PAE) polymers of low molecular weight namely of between 2,000-50,000 g/mol and a soy protein or lignin in which the weight ratio of protein or lignin to PAE is from 100:0.1 to 0.1:100.
• PAE low molecular polyamidoatnine-epihalohydrins
• compositions as adhesives for binding wood materials, such as laminates, plywood, particle board, oriented strand board and fiberboard.
• the low molecular weight of the PAE used in the compositions can also be expressed by a low Reduced Specific Viscosity (RSV) of less than 0.3 dl/g.
• RSV Reduced Specific Viscosity
• These low mol. weight or low viscosity PAE's are to be differentiated from high molecular weight PAE's of the art which have mol. wt. of 100,000 g/mol or more.
• the lower adhesive viscosity provides better handling properties, as well as allowing for less water in the adhesive formulation. The lower viscosity provides for both ease of handling of the adhesive material and the pot life if the adhesive formulation.
• the invention is directed towards use of a low molecular weight thermosetting polyamidoamine-epichlorohydrin resin (PAE resin) in an adhesive composition comprising the PAE resins and protein or lignin.
• PAE resin polyamidoamine-epichlorohydrin resin
• the low molecular weight PAE resins have a lower viscosity which allows them to be prepared and handled at high solids contents without encountering problems with gelation stability.
• the lower viscosity PAE resins are also useful in providing a lower viscosity PAE/protein adhesive composition, compared to an adhesive formulation prepared with a high molecular weight PAE resin.
• the lower viscosity adhesive compositions provide several benefits that the use of higher molecular weight PAE resins do not. This reduced viscosity provides longer storage stability and an increased ability to distribute the adhesive. Lower viscosity also improves the pumping of the adhesive and allows the adhesive to be sprayed more easily at a higher solids content than a corresponding adhesive composition made with a high molecular weight PAE resin.
• PAE resins are a two step process.
• a polyamidoamine is first prepared by the polycondensation of a polyamine with a polycarboxylic acid or a polycarboxylic acid derivative.
• a polycarboxylic acid is an organic compound with at least two carboxylic acid (carboxylate) functional groups.
• the resulting polyamidoamine is then dissolved in water and is reacted in aqueous solution with epichlorohydrin to prepare the final PAE product.
• the viscosity of the PAE resin of the present invention is less than 75 cps at 20% solids measured at 25 0 C by Brookfield viscometer.
• the molecular weight of the PAE resin used in the present invention is less than 100,000 g/mol..
• the molecular weight is greater than 2,000 g/mol, preferably greater than 5,000.
• the molecular weight is from about 5,000 to 80,000 g/mol, more preferably from about 10,000 to about 80,000 g/mol.
• the Reduced Specific Viscosity (RSV) of the PAE resin of the present invention is less than 0.3 dL/g more preferable less than 0.25 dL/g measured at 2% concentration in IM ammonium chloride at 25°C.
• RSV is a measurement of a polymer's solution viscosity that correlates directly to its molecular weight.
• the RSV can range from 0.0500 to 0.300 dL/g.
• the viscosity of a 20% solids aqueous solution of the PAE resin can range from 85 cps to less than 15 cps, such as 10 cps or 5 cps.
• the polyamidoamine is typically prepared by heating a polycarboxylic acid with a polyamine at a temperature of 125-200 0 C for 1 to 10 hours while collecting the water of condensation produced in the reaction, at atmospheric pressure. Where a reduced pressure is employed, lower temperatures such as 75 0 C to 150 0 C may be utilized. At the end of this reaction, the resulting product is dissolved in water, at a concentration of about 20 to 80% by weight total polymer solids, more typically at a concentration of about 30 to 70% and most typically at a concentration of about 40 to 60%.
• a diester can be used instead of a diacid to produce the polyamidoamine.
• the polymerization can be conducted at a lower temperature, preferably about 100-175 0 C at atmospheric pressure.
• the byproduct will be an alcohol, the type of alcohol depending upon the identity of the diester. For instance, where a dimethyl ester is employed the alcohol byproduct will be methanol, while ethanol will be the byproduct obtained from a diethyl ester. Where a reduced pressure is employed, lower temperatures such as 75°C to 150 0 C may be utilized.
• dicarboxylic acids and/or derivatives are used for the preparation of polyamidoamines s, although polycarboxylic having more than two carboxylate groups may be used.
• Suitable polycarboxylic acids include but are not limited to malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid , N,N,N',N'- ethylenediaminetetraacetate, 1 ,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) and 1,2,4,5-
• Polycarboxylic acid derivatives may also be used to prepare the polyamidoamine. These derivatives can be carboxylate esters, acid halides or acid anhydrides. These derivatives are typically more reactive towards amines than the corresponding carboxylic acid, so the reaction conditions to make polyamidoamines using carboxylic acid derivatives are generally milder than the conditions used to prepare polyamidoamines from polycarboxylic acids and polyamines.
• esters of the polycarboxylic acids are employed to produce the polyamidoamine to make the PAE used in the invention.
• the methyl or ethyl esters are typically used.
• the alcohol byproduct methyl alcohol or ethyl alcohol
• a strongly basic catalyst such as sodium methoxide can be employed in the synthesis of the polyamidoamides from polycarboxylic esters and polyamines.
• Particular esters of polycarboxylic acids which are suitable include dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate and diethyl glutarate.
• Suitable acid anhydrides that may be used to prepare the polyamidoamine include, but are not limited to, succinic anhydride, maleic anhydride, N,N,N',N'- ethylenediaminetetraacetate dianhydride, phthalic anhydride, mellitic anhydride and pyromellitic anhydride and mixtures thereof.
• a polycarboxylic acid halide is reacted with the polyamine to form a polyamidoamine.
• Particularly suitable are the polycarboxylic acid chlorides. In this case the reaction can be performed at very low temperatures.
• Appropriate polycarboxylic acid halides can be prepared from polycarboxylic acids by their reaction with thionyl chloride or phosphorus trichloride. Examples include, but are not limited to, adipoyl chloride, glutaryl chloride, and sebacoyl chloride.
• a single polycarboxylic acid or derivative thereof may be used in the polyamidoamine synthesis as well as mixtures of polycarboxylic acids. In addition, mixtures of polycarboxylic acids and derivatives of polycarboxylic acids are also suitable for use in this reaction.
• a variety of polyamines may be used in preparing the polyamidoamine. These include the general class of polyalkylenepolyamines which can be polyethylene polyamines, polypropylene polyamines, polybutylene polyamines, polypentylene polyamines, polyhexylene polyamines, and mixtures thereof.
• the polyalkylenepolyamines contemplated for use may be represented as polyamines in which the nitrogen atoms are linked together by groups of the formula C n Hb n where n is a small integer greater than unity and the number of such groups in the molecule ranges from two up to about eight.
• the nitrogen atoms may be attached to adjacent carbon atoms in the group — C n H 2n — or to carbon atoms further apart, but not to the same carbon atom.
• polyalkylenepolyarnine employed in the claims, therefore, refers to and includes any of the polyalkylenepolyamines referred to above or to a mixture of such polyalkylenepolyamines and derivatives thereof.
• Additional polyamines that are suitable for use include, but are not limited to, bis- hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine (MBAPA), aminoethyl- piperazine (AEP) and other polyalkylenepolyamines (e.g., spermine, spermidine).
• the polyamines are diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and dipropylenetriamine (DPTA).
• diamines When diamines are used in the synthesis of a polyamidoamine, they do not contribute to amine functionality in the final product, since both ends have reacted to form amide linkages. This has the effect of "diluting out” the amine functionality in the polymer, i.e. the amine equivalent molecular weight is increased. It is desirable, in some cases, to increase the spacing of secondary amino groups on the polyamide molecule in order to change the reactivity of the polyamide-epichlorohydrin complex. This can be accomplished by substituting a diamine such as ethylenediamine, propylenediamine, hexamethylenediamine and the like for a portion of the polyalkylene polyamine.
• a diamine such as ethylenediamine, propylenediamine, hexamethylenediamine and the like for a portion of the polyalkylene polyamine.
• polyalkylene polyamine may be replaced by molecularly equivalent amount of the diamine. Usually, a replacement of about 50% or less will serve the purpose.
• aminocarboxylic acids or lactams Similar to adding a diamine in a polyamidaomnine synthesis, aminocarboxylic acids or lactams increase the spacing between amine functional groups without contributing any amine functionality to the polymer. Appropriate aminocarboxylic acids containing at least three carbon atoms or lactams thereof are also suitable for use to increase spacing in the present invention. For example, 6-aminohexanoic acid and caprolactam are suitable additives for this purpose.
• the DP n is defined as the number-average degree of polymerization or the average number of monomer units in a polymer chain. Equation 1 defines the DP n in terms of the molar ratios of the components, assuming complete reaction of all functional groups.
• DP n (l+r)/(l-r) [L]
• a and B are the difunctional monomer components and C is the monofunctional component (end-capper).
• the quantity r will always be less than 1.
• a controlled molecular weight product is prepared by using specific amounts of a monofunctional reactant.
• the composition may be defined in terms of a polyamidoamine prepared from A parts dicarboxylic acid, B parts polyalkylenepolyamine and C parts monofunctional endcapping moiety, all parts given as molar quantities.
• A>B the endcapping moiety will be a monofunctional amine and C will equal about 2(A-B).
• B>A the endcapper will be a monofunctional acid and C will be equal to about 2(B-A).
• the polyamidoamines have a range of DP n of from about 3 to 50, more preferably a range of from about 3 to 40, and most preferably a range OfDP n is from about 3 to 30.
• temperatures and reaction times can be utilized in the reaction to produce the polyamidoamine. Temperatures of between about 125°C and 260 0 C are preferred, more preferably between about 155°C and 200 0 C 9 and the reaction mixtures are maintained at these temperatures for preferably between about 2 to 12 hours, more preferably between about 2 to 6 hours.
• Suitable monofunctional amines used as endcappers include, but are not limited to, monofunctional primary amines, including monoalkyl amines and monoalkanolamines, and monofunctional secondary amines, including dialkylamines and dialkanolamines.
• Monofunctional primary amines include, but are not limited to butylamine, ethanolamine (i.e., monoethanolamine, or MEA), cyclohexylamine, 2- methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, benzylamine, isopropanolamine (i.e., monoisopropanolamine), mono-sec-butanolamme, 2-amino-2-methyl- 1-propanol, tris(hydroxymethyl)aminomethane, tetrahydrofurfurylamine, furfurylamine, 3- amino-l,2-propanediol, 1 -amino- 1-deoxy-D-sorbitol, and 2-amino-2-ethyl- 1,3 -propanediol.
• ethanolamine i.e., monoethanolamine, or MEA
• cyclohexylamine 2- methylcyclohexylamine, 3-
• Monofunctional secondary amines include, but are not limited to, diethylamine, dibutylamine, diethanolamine (i.e., DEA), di-n-propylamine, diisopropanolamine, di-sec-butanolamine, and N-methylbenzylamine.
• Monofunctional carboxylic acids suitable for the endcapped polyamidoamine include, but are not limited to, benzoic acid, 2-hydroxybenzoic acid (i.e., salicylic acid), 3- hydroxybenzoic acid, acetic acid, phenylacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, oleic acid, ortho-toluic acid, meta-toluic acid, and para-toluic acid, ortho-methoxybenzoic acid, meta-methoxybenzoic acid, and para- methoxybenzoic acid.
• benzoic acid 2-hydroxybenzoic acid (i.e., salicylic acid), 3- hydroxybenzoic acid, acetic acid, phenylacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, oleic acid, ortho-toluic acid
• Mono-functional carboxylic acid esters suitable for the endcapped polyamidoamine include, but are not limited to, methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl phenyl acetate, and ethyl phenyl acetate.
• the volatility of the endcapping agent should be low enough so that the endcapping agent remains in the polymerization reaction at the temperature at which the reaction is being conducted. Particularly, when the polyamidoamine is prepared by thermally driven polycondensation, volatility is a significant feature of the endcapping agent; in this instance, an endcapping agent of lesser volatility is preferred.
• the boiling point of the endcapping agent should be high enough so that, at the temperature being employed to drive off the condensation product - i.e., water where a diacid reactant is used, and alcohol in the case of diester - the agent is not also removed.
• an amine excess prepared polyamidoamine can be used to prepare the PAE resins of the present invention.
• this route to obtaining the amine excess polyamidoamines uses an excess of polyalkylenepolyamine in the synthesis. This involves employing a reaction mixture wherein the ratio of total number of amine groups from the polyamine to the total number of carboxylic acid groups form the polycarboxylic acid is greater than 1 which results in a polyamidoamine with a preponderance of amine endgroups.
• the stoichiometry of polyamine to polycarboxylic acid can range from greater than about 1.0:1.0, on a molar basis, to 1.7: 1.0, more preferably, greater than about 1.01: 1.0 to 1.4:1.0.
• polyamidoamines having lower molecular weights than one would obtain by reacting an equimolar mixture under the same conditions.
• the polyamidoamines have a range of DP n of from about 3 to 50, more preferably a range of from about 3 to 40, and most preferably a range OfDP n is from about 3 to 30.
• Polyamidoamines disclosed in U.S. Patent 6,294,645 include endcapped materials and polyamidoamines in which the molecular weight is controlled by the extent of reaction.
• This patent is incorporated by reference and teaches how to control the molecular weight of a polyamidoamine by controlling the amount of distillate (water) removed during the polycondensation reaction of a dibasic acid and a polyamine.
• the molecular weight increases with increasing extent of reaction and amount of distillate produced. Lower molecular weights can be achieved by stopping the reaction before the theoretical amount of distillate has been produced.
• the second step in the synthesis of a PAE resin or polymer is the reaction of the polyamidoamine with epichlorohydrin to form a thermosetting cationic resin.
• the preparation of thermosetting PAE resins is well known.
• the synthesis of the PAE resin is typically conducted in aqueous solution.
• the polyamidoamine is reacted with epihalohydrin, preferably epichlorohydrin, at a temperature from about 25°C, to about 100 0 C and preferably between about 35°C to about 70 0 C.
• epihalohydrin preferably epichlorohydrin
• This reaction is preferably carried out in aqueous solution to moderate the reaction.
• pH adjustment can be performed to increase or decrease the rate of crosslinking.
• the product can be cooled to ambient temperature and then stabilized to permit storage by improving the gelation stability by adding sufficient acid to reduce the pH to less than about 6, preferably less than about 5, and most preferably less than about 4.
• Any suitable inorganic or organic acid may be used to stabilize the product. Examples include, but are not limited to, hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric acid, formic acid, phosphoric and acetic acid.
• Epichlorohydrin is the preferred epihalohydrin for use in the present invention.
• the present application refers to epichlorohydrin specifically in certain instances, however, the person skilled in the art will recognize that these teachings apply to epihalohydrin in general.
• Prior art has taught that viscosity build in the polyamidoamine-epichlorohydrin reaction should proceed to a certain point to determine when an acceptable molecular weight has been achieved in the final PAE resin. Higher molecular weight was taught to give greater strength characteristics. This teaching is in contrast to the present invention. In the present invention, the development of high molecular weight is not a desirable feature and measures are taken to prevent significant molecular weight increase from occurring.
• the main focus of the polyamidoamine-epichlorohydrin reaction as performed in the current invention is to functionalize the polyamidoamine with epichlorohydrin and generate the desired reactive functionality (aminochlorohydrin and/or azetidinium) without incurring an appreciable increase in molecular weight.
• a single cook step can be used for the polyamidoamine-epichlorohydrin reaction or a two step process can be used for the preparation of the low molecular weight PAE resin.
• epichlorohydrin is added to an aqueous solution of polyamidoamine and is allowed to react at a temperature of 35-70 0 C.
• An acid may be added to lower the pH of the reaction mixture and control the molecular weight increase of the PAE resin.
• Any suitable inorganic or organic acid may be used to stabilize the product. Examples include, but are not limited to hydrochloric acid, sulfuric acid, methanesulfonic acid, nitric acid, formic acid, phosphoric and acetic acid.
• the reaction is stopped by cooling, addition of dilution water and stabilization with an added acid before the resin develops any significant increase in molecular weight.
• a two-step process can be employed in order to better control the reaction and to reduce the levels of epichlorohydrin byproducts in the final product.
• the first step of this process is performed at low temperature (10-45 0 C) and is referred to as the alkylation step.
• epichlorohydrin reacts with amine groups in the polyamidoamine to form aminochlorohydrin functional groups.
• Epichlorohydrin is added to an aqueous solution of the polyamidoamine (typically 30-40% total solids before adding epichlorohydrin) and maintaining the reaction temperature at 10-45 0 C for 1 to 12 hours. During this time water may be added to slow the rate of crosslinking.
• the reaction is then diluted to an even lower solids content (20-30%) and the reaction is heated to 50-80 0 C to convert the aminochlorohydrin functional groups to azetidinium functional groups.
• a mineral acid H 2 SCM
• H 2 SCM may be added to adjust the pH (4.0 - 6.0) to reduce the rate of polymer crosslinking. This is typically done at 50-55 0 C, however it could be done earlier.
• the amount of mineral acid added may differ from the conventional synthesis of a PAE-epichlorohydrin resin, where crosslinking for increased molecular weight is desired.
• reaction pH values which inhibits the increase of molecular weight.
• the reaction is then terminated after a short period (about 15-90 minutes) at the required temperature or after achieving a set viscosity target.
• the reaction time at the elevated temperature is short compared to traditional preparations of PAE resins which have a cook time of 120-150 minutes at the elevated temperature.
• increased mineral acid use is a robust method of making lower molecular weight PAE' s, by utilizing proper viscosity monitoring it is possible to synthesis a PAE with similar properties using standard levels of mineral acid.
• Crosslinking is a step growth process so molecular weight roughly doubles with each crosslink. By killing the reaction before the molecular weight gained by crosslinking becomes significant a PAE with relatively low molecular weight can made using existing processes.
• Adhesive compositions of the present invention are prepared by combining the low molecular weight PAE resin with a protein and/or lignin.
• Suitable sources of protein include soy protein, blood meal, feather meal, keratin, gelatin, collagen, gluten and casein.
• the protein may be pretreated or modified to improve its solubility, dispersability and/or reactivity.
• U.S. patent 7,060,798, the entire content of which is herein incorporated by reference, teaches methods of modifying protein and their incorporation in to an adhesive.
• One particularly useful source of protein for the current invention is soy. Soy protein can commonly be obtained in the form of soy flour (about 50 wt.
• Lignin may be an industrial lignin such as Kraft lignin, obtained from the Kraft process of making cellulose pulp from wood.
• the combination of low molecular weight PAE resin and protein and/or lignin is prepared as an aqueous mixture wherein the components are combined and mixed with additional dilution water if required.
• Other additives may be included in the adhesive formulation such as extenders, viscosity modifiers, defoamers, biocides, and fillers such as wheat flour, tree bark flour, nut shell flour and corn cob flour.
• the components of the adhesive formulation are combined in a suitable mixer and are stirred until a homogeneous mixture is obtained.
• the adhesive compositions are typically prepared with solids contents in the range of 5 to 75 wt. %, more preferably in the range of 10 to 60 wt. % and most preferably in the range of 20 to 50 wt.
• the most effective ratio of PAE resin to protein and/or lignin in the adhesive composition will depend on the substrate being bonded, the type of protein and/or lignin used and the physicochemical properties of the PAE resin.
• the ratio of protein and/or lignin to PAE resin used in adhesive formulations will be preferably in the range of 100:1 to 0.1:1, more preferably in the range of 25:1 to 0.5:1 and most preferably in the range of lO:l to l : ⁇ .
• the pH of the adhesive mixture can be adjusted to control the reactivity of the thermosetting system.
• PAE resins are more reactive in the neutral to alkaline region (pH 6-9) and adjusting the pH to this range will give increasing reactivity as the pH ranges from about 6 to about 9. At some point above pH 9 thermosetting reactivity is reduced due to competing reactions such as hydrolysis of the polymer backbone.
• the adhesive compositions are thermosetting materials and as such are cured by the application of heat and optionally, pressure.
• Typical temperatures for curing the adhesive compositions are in the range of 50 to 250 0 C, more preferably in the range of 80 to 200 0 C and most preferably in the range of 100 to 150 0 C. Curing times at these temperatures can range from 30 seconds to one hour, more preferably from one minute to 30 minutes and most preferably from 2 minutes to 10 minutes.
• the adhesive composition can be added to a suitable substrate in the range of 1 to 25% by weight, preferably in the range of 1 to 10% by weight and most preferably in the range of 2 to 8% by weight.
• suitable substrates include, but are not limited to, a lignocellulosic material, pulp or glass fiber.
• the adhesive composition can be applied by the use of roller coating, knife coating, extrusion, curtain coating, foam coaters and spray coaters one example of which is the spinning disk resin applicator.
• Lignocellulosic materials such as wood, wood pulp, straw (including rice, wheat or barley), flax, hemp and bagasse can be used in making thermoset products from the invention.
• the lignocellulosic product is typically made by blending the adhesive with a substrate in the form of powders, particles, fibers, chips, flakes fibers, wafers, trim, shavings, sawdust, straw, stalks or shives and then pressing and heating the resulting combination to obtain the cured material.
• the moisture content of the lignocellulosic material should be in the range of 2 to 20% before blending with the adhesive composition.
• the adhesive compositions also may be used to produce plywood or laminated veneer lumber (LVL).
• the adhesive composition may be applied onto veneer surfaces by roll coating, knife coating, curtain coating, or spraying.
• a plurality of veneers are then laid-up to form sheets of required thickness.
• the mats or sheets are then placed in a heated press (e.g., a platen) and compressed to effect consolidation and curing of the materials into a board.
• Fiberboard may be made by the wet felted/wet pressed method, the dry felted/dry pressed method, or the wet felted/dry pressed method.
• the adhesive compositions can be used with substrates such as glass wool, glass fiber and other inorganic materials.
• substrates such as glass wool, glass fiber and other inorganic materials.
• the adhesive compositions can also be used with combinations of lignocellulosic and inorganic substrates.
• Example 1 Synthesis of a PAE resin using sulfuric acid to prevent molecular weight gain.
• a 500 mL 4 neck round bottom flask was charged with 106.8 g of a polyamidoamine made from diethylenetriamine (DETA) and adipic acid, and 45.8 g dilution water water.
• the polyamidoamine was prepared from an equimolar mixture of adipic acid and diethylenetriamine and had a total solids content of 48.69% in water.
• the reduced specific viscosity (RSV) of a 2% solution of the polymer in 1 N ammonium chloride was 0.143 dL/g as determined at 25.O 0 C by means of a Cannon automated capillary viscometer.
• a PoIyVISC or Auto VIS C model viscometer can be used for this purpose, both of which are available from Cannon Instrument Company, State College, PA.
• Flow times of the 2% polymer solution and the pure solvent are measured and the relative viscosity (Nrel) calculated.
• the reduced viscosity is calculated from the relative viscosity, and the reduced specific viscosity is calculated by dividing the reduced viscosity by the solution concentration.
• 22°C 22.58g epichlorohydrin was added all at once and the reaction was heated to 40 0 C. The reaction was held at that temperature for 190 minutes from the time of epichlorohydrin addition.
• the 1 H NMR spectra are acquired using BRUKER Avance spectrometers equipped with an inverse 5mm probe.
• a 1 H NMR operating frequency of 400 MHz (Avance 400) or 500 MHz (Avance 500) is sufficient for data collection.
• Electronic integration of the appropriate signals provides molar concentrations of the following alkylation components; polymeric aminochlorohydrins (ACH), and azetidinium ions (AZE). In order to calculate the concentrations of each of these species, the integral values must be placed on a one (1) proton basis.
• the spectral region between 1.72-1.25 ppm represents four (4) protons from the adipate portion of the diethylenetriamine-adipate backbone, hence the integral value is divided by 4.
• This value is used as the polymer common denominator (PCD) for calculation of the alkylation species.
• PCD polymer common denominator
• Water suppression pulse power level is 80 - 85dB — 60 Watt ⁇ H transmitter. Excess power will attenuate adjacent signals - USE "SOFT" PULSE
• SEC Size Exclusion Chromatography
• GPC Gel Permeation Chromatography
• the column temperature was 40 0 C and the differential refractive index (DBI) detector temperature was also 40 0 C.
• the calibration curve was constructed using a series of poly(vinyl pyridine) narrow molecular weight standards ranging in molecular weight from 1,090 to 1,650,000 Daltons obtained from Polymer Standards Service USA, Incorporated, Warwick, RI and a 202 molecular weight standard of 1-propylpyridinium bromide available from Aldrich Chemical Company, Milwaukee, WI. Samples for analysis were dissolved in the mobile phase at a concentration of 5 mg/mL and were filtered through a 45 ⁇ m pore size poly(vinylidene fluoride) filter before being analyzed.
• Example 2 Synthesis of a PAE resin starting with a lower molecular weight resin using a lower amount of sulfuric acid to prevent molecular weight gain.
• a quantity of 213.6g of a polyamidoamine prepared as disclosed in U.S. Patent 5,644,021, Example 4, having an RSV of 0.13 dL/g, measured as described in Example 1, and a total solids content of 50.0% in water was added to a 1 liter 4 neck round bottom flask. This polymer solution was diluted with 91.6 g of water and was warmed to 25 0 C. At that temperature epichlorohydrin (45.15 g) was added all at once and the reaction was heated to 40 0 C.
• Example 3 Synthesis of a PAE resin starting with a very low molecular weight resin using no sulfuric acid to prevent molecular weight gain.
• Comparative Example 4 High Molecular Weight Commercial PAE Resin (Comparative Example)
• Comparative example 4 is Kymene® 624, a commercial PAE resin that is available from Hercules Incorporated, Wilmington DE.
• a quantity of 213.6g of the polyamidoamine described in Example 1 was added to a 1 L 4-necked round bottom flask with 91.54 g dilution water and was warmed to 25 0 C. At that temperature epichlorohydrin (45.15 g) was added all at once and the reaction was heated to 40 0 C. The reaction was held at that temperature for 190 minutes from the time of the epichlorohydrin addition. Additional water (340.4 g) was then added to dilute the reaction to 22% total solids and the reaction was heated to cook temperature (65 0 C) in 30 minutes. After 10 minutes into the heating concentrated H2SO4 (1.8 g) was added to a pH of 6.75.
• Example 7 Preparation of polyamidoamine (PAA) from dimethyl glutarate (DMG) and diethylenetriamine (DETA) excess
• PAA polyamidoamine
• DMG dimethyl glutarate
• DETA diethylenetriamine
• the product had a total solids content of 50.18% and had a reduced specific viscosity (RSV) of 0.1370 dL/g, measured as described in Example 1.
• the material had a pH of 11.71 and had a Brookfield viscosity of 343 cPs measured at 60 rpm and 25 0 C with a #62 spindle using a Brookfield LV DV-E viscometer.
• PAA Polyamidoamines
• the reaction was performed in a 1 liter resin kettle fitted with a distillation receiver, mechanical stirrer, thermocouple and heating mantle with a temperature controller.
• To the reaction vessel was charged 371.4 Ig diethylenetriamine (DETA) followed by 438.42g adipic acid (AA) through a powder funnel.
• DETA diethylenetriamine
• AA adipic acid
• the reaction temperature was set for 125°C and was held there for 20 minutes. A slight reflux was observed at this point.
• the temperature set point was then increased to 150 0 C and was held at 150 0 C for 20 minutes.
• the set point was then increased to 170 0 C. Distillate began coming over at 159°C.
• PAA Polyamidoamines
• PAA Polyamidoamines
• AA adipic acid
• DPTA dipropylenetriamine
• Examples 21-25 are DMG-MBAPA excess polyamidoamines that were made in a similar manner as Example 7.
• the product had a total solids content of 50.28% and had a reduced specific viscosity (RSV) of 0.1159 dL/g, measured as described in Example 1. measured at a concentration of 2.0 wt. % in 1.0 M ammonium chloride using a Canon viscometry unit The reduced viscosity of a 2% solution of the polymer in 1 N ammonium chloride was determined at 25.0 0 C by means of a Cannon automated capillary viscometer. A PoIyVISC or Auto VISC model viscometer can be used for this purpose, both of which are available from Cannon Instrument Company, State College, PA. Flow times of the 2% polymer solution and the pure solvent are measured and the relative viscosity (Nrel) calculated.
• RSV specific viscosity
• the reduced viscosity is calculated from the relative viscosity, and the reduced specific viscosity is calculated by dividing the reduced viscosity by the solution concentration.
• the material had a pH of 10.26 and had a Brookfield viscosity of 342 cPs. The Brookf ⁇ eld viscosity was measured on the product at the solids reported (50.28%) measured at 60 rpm and 25°C with a #62 spindle using a Brookfield LV DV-E viscometer.
• Examples 27-38 Illustrate the preparation of PAE resins from polyamidoamines prepared with an amine excess.
• Example 27 PAE resin prepared from a 1.1/1.0 DETA/DMG Polyamidoamine [0080] The reaction was performed in a 4-necked 1 ,000 mL jacketed flask fitted with a condenser, thermocouple, pH meter, mechanical stirrer and heated with a circulating water bath. The reaction vessel was charged with 174.02g of polyamidoamine (Example 7) and 9 Ig of dilution water. To this stirred solution was added 48.58 g of epichlorohydrin. The theoretical total solids content of the reaction was 43.4% at this point. The reaction mixture was heated to 40 0 C for three hours using the circulating water bath. An initial exotherm to 42.7°C was observed.
• Example 28-38 PAE resins prepared from the amine excess polyamidoamines.
• PAE resins were prepared from the amine excess polyamidoamines. These materials were prepared in a manner similar to the procedure used to synthesize Example 27. The reaction conditions and product properties for these resins are shown in Table 6. All of these examples were heated in the first step to 40 0 C for three hours. In the second cook step Examples 28-33 were held at 65°C for one hour.
• PAE Resins Prepared from Amine Excess Polyamidoamines (PAmAm)
• Example 39 was made with the PAE resin of Example 4. (Kymene® 624 PAE resin available from Hercules Incorporated, Wilmington DE, comparative example.)
• Example 40 was made with the PAE resin of Example 1.
• Example 41 was made with the PAE resin of Example 2.
• Example 42 was made with the PAE resin of Example 3.
• Example 43 was made with the PAE resin of Example 5.
• Example 44 was made with the PAE resin of Example 6.
• PAE resin (20% in water, 11.25 g) was diluted with water (23 g) in a 100 mL beaker.
• Soy Flour (Cargill Prolia® 100/90, available from Cargill Incorporated, Minneapolis
• This reduced viscosity is a useful feature in the use and application of these materials as adhesives.
• Example 46-48 had significantly lower viscosity than the formulation made with the high molecular weight PAE resin (Example 45).
• the dry lap shear strength of Examples 46-48 were similar to the dry lap shear for Example 45.
• the wet shear strength of the formulations made with the low viscosity PAE resins tended to be lower than the wet shear strength of the formulation made with the high molecular weight PAE resin.
• Example 50-53 had significantly lower viscosity than the formulation made with the high molecular weight PAE resin (Example 49).
• the dry and wet lap shear strength of Examples 50 was similar to the dry and wet lap shear for Example 49.
• Examples 51-53 showed similar dry shear values as Comparative Example 49 and had somewhat lower wet shear strength than Comparative Example 49.
• Adhesive formulations with Cargill Prolia 100/90 soy flour were prepared. Table 9. Adhesive Formulations Made From PAE Resins and Soy Flour

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