WO2010065758A2 - Adhésifs à base de soja - Google Patents

Adhésifs à base de soja Download PDF

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Publication number
WO2010065758A2
WO2010065758A2 PCT/US2009/066614 US2009066614W WO2010065758A2 WO 2010065758 A2 WO2010065758 A2 WO 2010065758A2 US 2009066614 W US2009066614 W US 2009066614W WO 2010065758 A2 WO2010065758 A2 WO 2010065758A2
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WO
WIPO (PCT)
Prior art keywords
curing agent
soy protein
reaction
lignocellulosic
epichlorohydrin
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Application number
PCT/US2009/066614
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English (en)
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WO2010065758A3 (fr
Inventor
Kaichang Li
Original Assignee
State Of Oregon Acting By And Through The State Board Of Higher Educ. On Behalf Of Oregon State Univ
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Application filed by State Of Oregon Acting By And Through The State Board Of Higher Educ. On Behalf Of Oregon State Univ filed Critical State Of Oregon Acting By And Through The State Board Of Higher Educ. On Behalf Of Oregon State Univ
Publication of WO2010065758A2 publication Critical patent/WO2010065758A2/fr
Publication of WO2010065758A3 publication Critical patent/WO2010065758A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/13—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/14—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/08—Coating on the layer surface on wood layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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

Definitions

  • the present disclosure relates to soy adhesives for making lignocellulosic composites.
  • Lignocellulosic-based composites are formed from small dimension pieces of cellulosic material that are bonded with an adhesive (i.e., a binder).
  • an adhesive i.e., a binder
  • solid wood is fragmented into smaller pieces such as strands, fibers, and chips.
  • An adhesive composition then is added to the wood component.
  • the resulting mixture is subjected to heat and pressure resulting in a composite.
  • the adhesive mix typically is the only non-lignocellulosic component.
  • PF and UF resins are phenol-formaldehyde resins (PF) and urea-formaldehyde resins (UF).
  • VOC volatile organic compounds
  • CARB California Air Resources Board
  • PF and UF resins are made from petroleum-derived products. The reserves of petroleum are naturally limited.
  • Soy protein was used as a wood adhesive for the production of plywood from the 1930' s to the 1960's. Petroleum-derived adhesives replaced soy protein adhesives due to the relatively low bonding strength and water resistance of soy protein adhesives.
  • soy protein is an inexpensive, abundant, renewable material that is environmentally acceptable.
  • PAE polyamidoamine-epichlorohydrin adduct
  • One embodiment of a method for making a lignocellulosic composite disclosed herein includes : applying (i) soy protein and (ii) a curing agent to at least one lignocellulosic substrate; and bonding the composition-applied substrate to at least one other lignocellulosic substrate, wherein the curing agent is made by a method comprising: reacting (i) ammonia with (ii) epichlorohydrin, a chlorinated propanol or a mixture thereof at a temperature of 50 to 6O 0 C.
  • the curing agent for making the lignocellulosic composite is prepared by reacting (i) ammonia with (ii) epichlorohydrin, a chlorinated propanol, or a mixture thereof to produce an intermediate and subsequently heating the intermediate to produce a curing agent.
  • the curing agent is prepared in an aqueous medium.
  • An adhesive composition suitable for bonding lignocellulosic materials is prepared by mixing any of the curing agent embodiments with a soy protein.
  • the adhesive composition includes a base.
  • a lignocellulosic composite is prepared by applying soy protein and any of the curing agent embodiments to a lignocellulosic substrate, which then is bonded to another lignocellulosic substrate.
  • the lignocellulosic composite further includes a base and/or a boron compound.
  • a substantially formaldehyde-free composition is prepared from soy protein, a curing agent, and comminuted lignocellulosic materials.
  • Figure 1 is a graph depicting test results for one embodiment of an adhesive disclosed herein.
  • Embodiments of an adhesive composition can be made by reacting or mixing a soy protein with at least one substantially formaldehyde-free curing agent.
  • the substantially formaldehyde-free compound may provide both curing for the adhesive composition and adhesion to the lignocellulosic substrate.
  • the substantially formaldehyde-free compound may be a difunctional adhesion promoter in the sense that one compound can provide dual functions.
  • the curing agent is a reaction product of (ii) ammonia with (ii) epichlorohydrin and/or a chlorinated propanol.
  • the adhesive composition may be provided as a two-part system in which the protein comprises one part or package and the curing agent comprises the second part or package. All the parts or components of the composition may be in the form of aqueous solutions or dispersions. Thus, volatile organic solvents as carrier fluids can be avoided.
  • Soy protein is an exemplary protein for use in the presently described adhesives.
  • Soybeans contain about 38 wt% protein with the remaining portion comprising carbohydrates, oils, ash and moisture. Soybeans are processed to increase the amount of soy protein in the processed product.
  • Soy protein products of any form may be utilized in the disclosed adhesive compositions. The three most common soy protein products are soy flour, soy protein concentrate, and soy protein isolate (SPI). One difference between these products is the amount of soy protein.
  • soy flour may typically include approximately 45-55 wt% protein
  • soy protein concentrate includes at least about 65 wt% protein (dry weight)
  • SPI includes at least about 85 wt% protein (dry weight).
  • the soy protein is soy flour.
  • the curing agents are prepared from epichlorohydrin and/or chlorinated propanols, particularly 1,3-dichloropropanol or 1 ,2-dichloropropanol, and aqueous ammonia.
  • epichlorohydrin is manufactured from propylene. Propylene reacts with chlorine gas to form allyl chloride. The allyl chloride is converted to dichloropropanol with peroxide. Dichloropropanol reacts with sodium hydroxide to form epichlorohydrin, as shown below:
  • a curing agent is prepared by reacting epichlorohydrin, a chlorinated propanol, or a mixture thereof with aqueous ammonia (NH3).
  • epichlorohydrin or chlorinated propanol is reacted with ammonia at NHyepichlorohydrin or NHychlorinated propanol molar ratios ranging from 5:1 to 1 :5, more particularly from 2: 1 to 1 :3.
  • undesirable side reactions may occur in the presence of excess ammonia.
  • a mixture of epichlorohydrin (and/or chlorinated propanol) and aqueous ammonia is vigorously stirred in a sealed reaction at a predetermined temperature selected from 50 0 C to 60 0 C, particularly from 55 0 C to 60 0 C to produce, the curing agent.
  • the reaction is exothermic.
  • the reaction may be cooled to maintain a temperature range of 50 0 C to 60 0 C, particularly from 55 0 C to 60 0 C.
  • the reaction is considered complete when the initial heterogeneous reaction mixture becomes a homogeneous solution.
  • the reaction typically progresses for 20 minutes to 20 hours, although preferably the reaction is complete in 4 hours or less.
  • a mixture of epichlorohydrin (and/or chlorinated propanol) and aqueous ammonia is vigorously stirred in a sealed reaction at a predetermined temperature selected from 0 0 C to 65 0 C, such as from 25 0 C to 60 0 C to produce an intermediate product.
  • the reaction temperature is 30 to 45 0 C, more particularly 40 0 C. If the temperature is too low, the reaction is slow to occur. At temperatures over 65 0 C, side reactions, such as replacement of a chlorine atom with an amino group, may occur. The reaction is exothermic.
  • the reaction may be cooled to maintain a temperature range of 0 to 65 0 C, such as 25 to 60 0 C.
  • the reaction is considered complete when the initial heterogeneous reaction mixture becomes a homogeneous solution.
  • the reaction typically progresses for 20 minutes to 20 hours.
  • the intermediate product may include a mixture of different compounds.
  • the main products of this reaction may include compounds with the following formulas: N(CH 2 CHOHCH 2 Cl) 3 (compound (I)), HN(CH 2 OHCH 2 Cl) 2 and H 2 NCHOHCH 2 Cl.
  • compound (1) was the main product:
  • the intermediate product then is subjected to a second additional heating step to produce a final curing agent product.
  • the prepared intermediate is heated at a temperature selected from 65 0 C to 98 0 C, more particularly, from 70 0 C to 80 0 C.
  • the second heating step may occur at a pH selected from 6 to 14, particularly pH 8-10.
  • the second reaction is carried out for 20 minutes to 5 hours.
  • the resulting curing agent may have a solids content of 5 to 80, more particularly 25 to 60, wt%.
  • the second heating step may cause a portion of the intermediate product to cyclize.
  • the product (which may be a mixture of different compounds) of the second heating step may include at least one of the following compounds:
  • the intermediate product may be reacted further with ammonia and additional epichlorohydrin to produce compounds such as those shown below.
  • the intermediate product in a first step the intermediate product may be reacted with a molar excess (e.g., a 2 to 4-fold excess) of ammonia at 10 to 98 0 C for 1 to 24 hours to produce a second intermediate (4).
  • the second intermediate then can be reacted with a molar excess (e.g., a 4 to 10-fold excess) of epichlorohydrin at 10 to 98 0 C to produce a third intermediate (5).
  • the third intermediate may be further heated at 65 to 98 0 C to produce a final curing agent product (6).
  • At least one boron compound, a group IA oxide or hydroxide, or a group HA oxide or hydroxide may also be included as a base in the adhesive composition.
  • the boron compound may be any compound or material that includes at least one boron atom or species.
  • Group IA and group HA refer to the element classifications in the Periodic Table of the Elements. Although not bound by any theory, it is believed that a boron species not only acts as a base to buffer the pH of the adhesive, but also can potentially chelate with hydroxyl groups, thus serving as a crosslinking agent for the soy protein or lignin.
  • the group IA or group HA species can potentially facilitate the reactions between the curing agent and soy flour and the reactions between the curing agent and lignocellulosic components.
  • the metal ions of group IIA species can potentially chelate with a plurality of carboxylic acid groups, thus serving as a crosslinking agent for the soy protein or lignin.
  • the boron compound may be boric acid, a boron salt, or a borate ester.
  • boric acid, borate salts and borate esters can be produced from numerous other boron compounds, including without limitation, metaborates, acyl borates, anhydrous borates, borax, boron hydrides, and the like.
  • Specific examples of borate salts or borate esters include sodium borate, anhydrous sodium borate, sodium tetraborate, sodium boro formate and sodium borohydride.
  • boron compounds can be provided as various salts and in various hydration states, including without limitation, KB 5 ⁇ 2 O, Na 2 B 4 O 7 -IOH 2 O, Na 2 B 4 O r 5H 2 O, Mg 3 B 7 O 13 Cl, K 3 B 3 O 6 , CaB 2 O 4 , and the like.
  • About 0.1 to about 15 wt%, more particularly about 0.1 to about 5 wt% of the boron compound(s) may be included in the adhesive, based on the combined dry weight of soy protein and curing agent.
  • the group IA oxide or hydroxide or group IIA oxide or hydroxide may be a hydroxide or oxide of calcium, sodium or potassium.
  • Illustrative compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, or calcium oxide.
  • the amount of group IA oxide or hydroxide, or group IIA oxide or hydroxide added to the mixture may vary. For example, about 0.1 to about 20 wt%, more particularly about 0.1 to about 10 wt% of the base(s) may be included in the adhesive, based on the combined dry weight of soy protein and curing agent.
  • the adhesive composition also may include additives and fillers found in lignocellulosic adhesives such as bactericides, insecticides, silica, wax, wheat flour, tree bark flour, nut shell flour and the like.
  • the ingredients of the adhesive composition may be mixed together in any order and at standard temperature and pressure (i.e., about 25°C and about 1 atmosphere). Typically, the ingredients are water soluble or water dispersible.
  • the solids content of the resulting final adhesive mixture may be from 5 to 65 wt.%, more particularly from 25 to 50 wt %.
  • Each (or only one) part of the adhesive system could be provided to the end user in the form of a concentrate that is diluted by the end user to the appropriate mix ratios and solid contents.
  • the soy protein component, the curing agent, the base, and additives/fillers are mixed together a short time prior to use.
  • the composition may have an open time of up to about 5 days.
  • open time denotes the time from mixing of the two parts to the time at which the mixed composition cures to a point that it is no longer workable.
  • all the ingredients of the adhesive composition are pre-mixed together in a one-part system that is then supplied to an end user. In the one-part system, the adhesive composition can be applied to a substrate without the need for mixing together multiple different components.
  • the adhesive compositions are heat-curable.
  • heating the adhesive mixture forms covalent bonds between the individual molecules of the adhesive composition and covalent and/or hydrogen bonds between molecules of the adhesive mixture and the lignocellulosic particles.
  • curing typically occurs during the hot pressing step of the composite formation.
  • the cure temperature of the adhesive composition is tailored so that it coincides with the heating temperatures used in composite formation. Such cure temperatures may range, for example, from about 80 to about 220 0 C, more particularly from about 100 to about 160 0 C.
  • the adhesive mixture typically is not heated until after it has been applied to the lignocellulosic substrates.
  • Lignocellulosic composites that can be produced with the adhesives described herein include particleboard, plywood, oriented strand board (OSB), waferboard, fiberboard (including medium-density and high-density fiberboard), parallel strand lumber (PSL), laminated strand lumber (LSL), laminated veneer lumber (LVL), and similar products.
  • these composites are made by first blending comminuted lignocellulosic materials with an adhesive that serves as a binder to adhere the comminuted lignocellulosic materials into a unitary densified mass.
  • suitable lignocellulosic materials include wood, bamboo, straw (including rice, wheat and barley), flax, hemp and bagasse.
  • the comminuted lignocellulosic materials can be processed into any suitable substrate form and size such as chips, flakes, fibers, strands, wafers, trim, shavings, sawdust, straw, stalks, shives, and mixtures thereof.
  • the lignocellulosic materials are mixed together with the adhesive composition serving as a binder, and formed into a desired configuration to provide a pre-bonded assembly.
  • the pre-bonded assembly then is subjected to heat and elevated pressure to provide the lignocellulosic composite product.
  • the pre-bonded assembly may be subjected to temperatures of from about 120 to 225°C in the presence of varying amounts of steam, generated by liberation of entrained moisture from the lignocellulosic materials.
  • the amount of adhesive mixed with the lignocellulosic particles may vary depending, for example, upon the desired composite type, lignocellulosic material type and amount and specific adhesive composition. In general, about 1 to about 15, more particularly about 3 to about 10, weight percent adhesive may be mixed with the lignocellulosic material, based on the total combined weight of adhesive and lignocellulosic material.
  • the mixed adhesive composition may be added to the comminuted lignocellulosic particles by spraying or similar techniques while the lignocellulosic particles are tumbled or agitated in a blender or similar mixer. For example, a stream of the comminuted lignocellulosic particles may be intermixed with a stream of the mixed adhesive composition and then be subjected to mechanical agitation.
  • a lignocellulosic composite composition may be made by mixing together soy protein, the curing agent, and comminuted lignocellulosic materials.
  • the components may be mixed in order.
  • the soy protein and curing agent may be pre -mixed prior to mixing with the comminuted lignocellulosic materials.
  • the soy protein and comminuted lignocellulosic materials may be pre -mixed, or the curing agent and the comminuted lignocellulosic materials may be pre -mixed.
  • the adhesive compositions also may be used to produce layered lignocellulosic composites.
  • Soy protein and a curing agent may be applied to at least one lignocellulosic substrate, which is then bonded to at least one other lignocellulosic substrate.
  • a base and borate also may be applied to the lignocellulosic substrate.
  • the soy protein, curing agent, base and borate may be mixed together and then applied to the lignocellulosic composite.
  • the adhesive compositions can 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.
  • 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 presently disclosed adhesives provide a strong bond between the lignocellulosic substrates.
  • the adhesives also provide structural composites with high mechanical strength.
  • the curing agent and the adhesive compositions are substantially free of formaldehyde (including any compounds that may degenerate to form formaldehyde).
  • the curing agent and the adhesive compositions do not contain any formaldehyde (and formaldehyde- generating compounds) that is detectable by conventional methods or, alternatively, the amount of formaldehyde (and formaldehyde-generating compounds) is negligible from an environmental and workplace regulatory standpoint.
  • the specific examples described below are for illustrative purposes and should not be considered as limiting the scope of the appended claims.
  • the reaction mixture was initially milky and then became a homogeneous solution.
  • the resulting curing agent was designated as CA#1.
  • the CA#1 was acidified with 1 N sulfuric acid to pH 3 for long term storage.
  • the CA#1 was treated at 75 0 C for one hour to form a new curing agent (CA#2).
  • the acidified CA#1 was adjusted to pH 9.5 with 1 N NaOH before the heat treatment at 75 0 C.
  • Soy flour (100 mesh and protein dispersibility index 90), CA#1, sodium hydroxide and water were mixed in a KitchenAid mixer for 5 minutes.
  • the dry weight ratio of soy flour/C A# 1 was 7:1.
  • the dry weight ratio of NaOH/(soy flour + CA#1) was 0.03:1.
  • the total solids content of the adhesive was 36 %.
  • Soy flour (100 mesh and protein dispersibility index 90), CA#2, sodium hydroxide and water were mixed in a KitchenAid mixer for 5 minutes.
  • the dry weight ratio of soy flour/C A#l was 7:1.
  • the dry weight ratio of NaOH/(soy flour + CA#1) was 0.03:1.
  • the total solids content of the adhesive was 36 %.
  • Either soy flour/C A#l adhesive or soy flour/C A#2 adhesive was applied to two sides of a yellow-poplar or aspen veneer (2 ft x2 ft; moisture content 12%) by a roller coater with the adhesive spread rate of about 8 mg/cm 2 .
  • the adhesive-coated veneer was stacked between two uncoated veneers with the grain directions of two adjacent veneers perpendicular to each other.
  • the stacked 5-ply veneers were put on a table for 5 minutes, cold-pressed at 100 psi for 5minutes, put on a table again for 5 minutes and hot-pressed at 150 psi at 130 0 C for 6 minutes. After hot-press, the panel was stored at ambient environment for at least 24 hours before it was evaluated for its shear strength and water-resistance.
  • Example 5 Determination of water resistance
  • the water-resistance of the plywood panels was determined with a three- cycle soak test in accord with the American National Standard for Hardwood and Decorative Plywood; Hardwood Plywood & Veneer Association; 2004
  • ANSI/HP VA HP-I is the commonly accepted standard for evaluating the water-resistance of interior plywood. The following is a detailed testing procedure defined by the standard. Twenty plywood specimens (2 in x 5 in) cut from each plywood panel were soaked in water at 24 ⁇ 3 0 C for 4 hours, and then dried at 49 0 C to 52 0 C for 19 hours. All specimens were inspected to see whether they were delaminated. This soaking/drying cycle was repeated until three cycles were completed.
  • a plywood panel meets water-resistance requirement for interior applications if 95% of the specimens, i.e., 19 out of the 20 specimens do not delaminate after the first soaking/drying cycle and 85% of specimens, i.e., 17 out of 20 specimens do not delaminate after the third soaking/drying cycle.
  • the ANSI/HP VA HP-I specifically provides the following definition of delamination: any continuous opening between two layers has to be longer than two inches and deeper than 0.25 inch and wider than 0.003 inch.
  • Table 1 illustrates the results. The panels formed with CA#1 did not meet the standard. After the second cycle, 5-6 specimens had delaminated. However, panels formed with the heat-treated curing agent CA#2 met the standard with none of the specimens delaminating after three cycles. Table 1
  • Curing agents and soy-based adhesives were prepared as described in Examples 1 and 2.
  • Five-ply plywood panels were prepared with yellow poplar veneer under hot-press conditions of 130 0 C, 150 psi and 6 minutes.
  • the following two-cycle boil test can be used to evaluate whether plywood panels can meet one of the water-resistance requirements for exterior applications.
  • the 76 mm by 76 mm (3 inches by 3 inches) specimens are submerged in boiling water for 4 hours and then dried at a temperature of 63 ⁇ 3 0 C (145 ⁇ 5 0 F) for 20 hours with sufficient air circulation to lower the moisture content of the specimens to a maximum of 12 percent of the ovendry weight.
  • Table 2 illustrates the results of the two-cycle boil test of plywood formed with CA#1 with all eight specimens delaminating after the test. Dramatically improved results were obtained with the heat-treated curing agent CA#2. None of the specimens from panel 1 delaminated after the test. Four out of eight specimens from panel 2 delaminated.
  • Soy flour (7% moisture content) was provided by Cargill Incorporated (Minneapolis, MN); Epichlorohydrin(99%) and ammonium hydroxide (28%-30% wt% solution OfNH 3 in water) were purchased from Acros Organics(Morris Plains, NJ); Yellow-poplar, maple, white fir, pine and aspen veneer were a gift from Columbia Forest Products (Portland, OR).
  • CA curing agents
  • Ammonium hydroxide (28-30%, 89.44 g, 1.5mol, 102 mL) and epichlorohydrin (99%, 456 g, 4.5mol, 354 mL) were added to the water (150 mL) and stirred at 600RPM in a 2 L resin kettle equipped with a condenser, a thermometer and an inside cooling coil which was connected with a cooling circulator.
  • the temperature of the mixture increased slowly at the beginning and then dramatically went up as time passed. When the temperature reached the predetermined one, turned on the cooling circulator and maintained the temperature by switching on or off the circulator.
  • the mixture was milky once stirred because epichlorohydrin is not soluble in water. When the mixture became clear, it was further stirred for half hour.
  • the product was stored at room temperature. The solids content of the product is about 50% after extraction with ethyl acetate.
  • the resulting CA was acidified with 1 N sulfuric acid to pH 3 for long term storage.
  • Example 8 The CA prepared from the Example 7 was treated at 75 0 C for one hour to form a new CA. If an acidified CA was used for the heat treatment, it was adjusted to pH 9.5 with 1 N NaOH before the heat treatment at 75 0 C.
  • the water-resistance of the plywood panels was determined with a three-cycle soak test in accord with the American National Standard for Hardwood and Decorative Plywood; Hardwood Plywood & Veneer Association; 2004 (ANSI/HP VA HP-I).
  • the three-cycle soak test is the commonly accepted standard for evaluating the water-resistance of interior plywood (the type II plywood). The following is a detailed testing procedure defined by the standard. Twenty plywood specimens (2 in x 5 in) cut from each plywood panel were soaked in water at 24 ⁇ 3 0 C for 4 hours, and then dried at 49 0 C to 52 0 C for 19 hours. All specimens were inspected to see whether they were delaminated. This soaking/drying cycle was repeated until three cycles were completed.
  • a plywood panel meets water-resistance requirement for interior applications if 95% of the specimens, i.e., 19 out of the 20 specimens do not delaminate after the first soaking/drying cycle and 85% of specimens, i.e., 17 out of 20 specimens do not delaminate after the third soaking/drying cycle.
  • the ANSI/HP VA HP-I specifically provides the following definition of delamination: any continuous opening between two layers has to be longer than two inches and deeper than 0.25 inch and wider than 0.003 inch.
  • the reaction of epichlorohydrin and ammonia in water is highly exo-thermal.
  • the reaction temperature has to be properly controlled to obtain a useful CA.
  • the reaction time is defined as the time between the beginning of mixing the reaction mixture and the time when the reaction mixture became a clear homogeneous solution.
  • the effect of the reaction temperature on the reaction time is shown in Table 3. The reaction time decreased dramatically with the increase of the reaction temperature.
  • NaOH may be helpful for generating azetidinium groups and epoxy groups, so the effect of addition of NaOH in preparation of SF-CA adhesives was studied.
  • the curing agent prepared at 50 0 C without further heat treatment was used to make plywood panels. Based on our previous experience on making plywood panels, aspen has smaller variability than other species like yellow poplar. Therefore aspen was used to investigate the effect of NaOH.
  • the results were shown in Table 4 and Figure 1.
  • the panels with NaOH had no failed specimens after the three-cycle soak test.
  • One panel without NaOH had no failed specimens and another had three failed specimens after the three-cycle soak test. But all four panels passed the three-cycle soak test.
  • the dry shear strength of plywood panels with NaOH was significantly higher than that of panels without NaOH. Therefore, NaOH (3 wt% based on dry weight of SF and CA) was included in SF-CA adhesives in all subsequent investigations.
  • Heat treatment of a prepared CA may be helpful to form an azetidinium group that is a key functional group reacting with soy protein.
  • Effects of a second heat treatment of CA at 75 0 C for one hour and the reaction temperature on the water resistance of plywood panels bonded with SF-CA adhesives are shown in Table 5 and Table 6.
  • the further heat treatment of the CA did not make any difference on the water resistance of 5-ply aspen plywood, i.e., all plywood panels passed the three-cycle soak test.
  • the heat treatment greatly improved the water resistance of 5-ply yellow poplar plywood panels.
  • Results from Table 5 revealed that the second step heat treatment of CA prepared in the reaction temperature range of 30 0 C to 45 0 C is beneficial.
  • the reaction time includes 30 min of extra stirring time at a predetermined temperature after the solution became clear.
  • Table 4 The effect of addition of NaOH on the water resistance of 5-ply aspen plywood

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention porte sur des modes de réalisation d'un procédé et d'une composition pour fabriquer des agents de durcissement, des adhésifs à base de soja comprenant les agents de durcissement, et des composites lignocellulosiques fabriqués avec les adhésifs. Un mode de réalisation d'un procédé de fabrication d'un composite lignocellulosique comprend les opérations consistant à : appliquer (i) une protéine de soja et (ii) un agent de durcissement sur au moins un substrat lignocellulosique; et lier le substrat sur lequel la composition est appliquée à au moins un autre substrat lignocellulosique, l'agent de durcissement étant obtenu par un procédé comprenant les opérations consistant à : faire réagir (i) de l'ammoniac avec (ii) de l'épichlorhydrine, un propanol chloré ou un mélange de ceux-ci à une température de 50 à 60°C. Dans un autre mode de réalisation, l'agent de durcissement pour fabriquer le composite lignocellulosique est préparé par réaction (i) d'ammoniac avec (ii) l'épichlorhydrine, un propanol chloré, ou un mélange de ceux-ci pour produire un intermédiaire, et à chauffer ensuite l'intermédiaire pour produire un agent de durcissement.
PCT/US2009/066614 2008-12-03 2009-12-03 Adhésifs à base de soja WO2010065758A2 (fr)

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WO2013112445A1 (fr) * 2012-01-23 2013-08-01 Hercules Incorporated Procédé pour la préparation de composite de bois à partir de farine de soja
US8519031B2 (en) 2009-03-06 2013-08-27 Biopolymer Technologies, Ltd. Protein-containing emulsions and adhesives, and manufacture and use thereof
US8916668B2 (en) 2010-06-07 2014-12-23 Biopolymer Technologies, Ltd. Protein-containing adhesives, and manufacture and use thereof
WO2016141126A1 (fr) 2015-03-04 2016-09-09 Solenis Technologies, L.P. Procédé de fabrication de composites lignocellulosiques
US9873823B2 (en) 2012-07-30 2018-01-23 Evertree Protein adhesives containing an anhydride, carboxylic acid, and/or carboxylate salt compound and their use
US10125295B2 (en) 2011-09-09 2018-11-13 Evertree Protein-containing adhesives, and manufacture and use thereof
US10160842B2 (en) 2009-03-06 2018-12-25 Evertree Protein-containing foams, manufacture and use thereof
US10266694B2 (en) 2015-03-12 2019-04-23 Auburn University Use of soy flour in resin formulations used to manufacture engineered wood composites
KR20190096719A (ko) * 2018-02-09 2019-08-20 주식회사 지피피 난연 시트지, 그 제조방법 및 그 제조장치
CN110499141A (zh) * 2019-08-29 2019-11-26 贵州大学 一种生物质交联剂改性油茶油饼胶黏剂及制备方法和应用
US10899039B2 (en) 2016-03-16 2021-01-26 Auburn University Soy-modified resins for bonding wood
US11028298B2 (en) 2011-09-09 2021-06-08 Evertree Protein-containing adhesives, and manufacture and use thereof
CN114774077A (zh) * 2022-04-28 2022-07-22 南宁市匠心鸣居建筑材料有限公司 一种胶合板用胶粘剂的制备方法

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US7252735B2 (en) * 2002-05-13 2007-08-07 State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives
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WO2005113700A1 (fr) * 2004-04-20 2005-12-01 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Adhésifs ligno cellulosiques libres de formaldéhyde et composites constitués à partir des adhésifs

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US9909044B2 (en) 2009-03-06 2018-03-06 Evertree Protein-containing emulsions and adhesives, and manufacture and use thereof
US8519031B2 (en) 2009-03-06 2013-08-27 Biopolymer Technologies, Ltd. Protein-containing emulsions and adhesives, and manufacture and use thereof
US10745601B2 (en) 2009-03-06 2020-08-18 Evertree Protein-containing emulsions and adhesives, and manufacture and use thereof
US9309444B2 (en) 2009-03-06 2016-04-12 Biopolymer Technologies, Ltd. Protein-containing emulsions and adhesives, and manufacture and use thereof
US10160842B2 (en) 2009-03-06 2018-12-25 Evertree Protein-containing foams, manufacture and use thereof
US9416303B2 (en) 2010-06-07 2016-08-16 Biopolymer Technologies, Ltd. Protein-containing adhesives, and manufacture and use thereof
US9816019B2 (en) 2010-06-07 2017-11-14 Evertree Protein-containing adhesives, and manufacture and use thereof
US10465103B2 (en) 2010-06-07 2019-11-05 Evertree Protein-containing adhesives, and manufacture and use thereof
US10913880B2 (en) 2010-06-07 2021-02-09 Evertree Protein-containing adhesives, and manufacture and use thereof
US8916668B2 (en) 2010-06-07 2014-12-23 Biopolymer Technologies, Ltd. Protein-containing adhesives, and manufacture and use thereof
US10125295B2 (en) 2011-09-09 2018-11-13 Evertree Protein-containing adhesives, and manufacture and use thereof
US11072731B2 (en) 2011-09-09 2021-07-27 Evertree Protein-containing adhesives, and manufacture and use thereof
US11028298B2 (en) 2011-09-09 2021-06-08 Evertree Protein-containing adhesives, and manufacture and use thereof
WO2013112445A1 (fr) * 2012-01-23 2013-08-01 Hercules Incorporated Procédé pour la préparation de composite de bois à partir de farine de soja
US9873823B2 (en) 2012-07-30 2018-01-23 Evertree Protein adhesives containing an anhydride, carboxylic acid, and/or carboxylate salt compound and their use
US10526516B2 (en) 2012-07-30 2020-01-07 Evertree Protein adhesives containing an anhydride, carboxylic acid, and/or carboxylate salt compound and their use
WO2016141126A1 (fr) 2015-03-04 2016-09-09 Solenis Technologies, L.P. Procédé de fabrication de composites lignocellulosiques
US10266694B2 (en) 2015-03-12 2019-04-23 Auburn University Use of soy flour in resin formulations used to manufacture engineered wood composites
US10899039B2 (en) 2016-03-16 2021-01-26 Auburn University Soy-modified resins for bonding wood
KR102013119B1 (ko) 2018-02-09 2019-08-22 (주)지피피 난연 시트지, 그 제조방법 및 그 제조장치
KR20190096719A (ko) * 2018-02-09 2019-08-20 주식회사 지피피 난연 시트지, 그 제조방법 및 그 제조장치
CN110499141A (zh) * 2019-08-29 2019-11-26 贵州大学 一种生物质交联剂改性油茶油饼胶黏剂及制备方法和应用
CN114774077A (zh) * 2022-04-28 2022-07-22 南宁市匠心鸣居建筑材料有限公司 一种胶合板用胶粘剂的制备方法
CN114774077B (zh) * 2022-04-28 2023-12-15 黑龙江佰嘉生物质材料有限公司 一种胶合板用胶粘剂的制备方法

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