PREPARATION OF LIGNOCELLULOSIC-ISOCYANATE MOLDED COMPOSITIONS USING A TERPOLYMER OF A FUNCTIONAL POLYSILOXANE-ISOCYANATE-CARBOXYLIC ACID OR SALT THEREOF AS RELEASE AGENT

Abstract: In the compression molding of lignocellulosic composite articles, such as particle or flake board, in which polyisocyan­ ate binder systems are employed, a terpolymer of a hydroxy- or carboxy- polysiloxane, an isocyanate and a hydroxyl substituted monocarboxylic acid or metal salt thereof is employed as a release agent on the mold surface or surfaces to give multiple release. Optionally, organopolysiloxane fluids may be employed along with the terpolymer release agent as a diluent.

Description: BACKGROUND OF THE INVENTION The present invention relates to the compression .molding of lignocellulosic materials into composite bodies, sheets and the like and more particularly to a method for the preparation of particle or flake board with a polyisocyanate binder and the use of a terpolymer which is the reaction product of a functional polysiloxane, an isocyanate, and a hydroxyl substituted monocarboxylic acid or metal salt thereof as a release agent capable of providing an ease of release and multiple release from the forming mold surfaces. The molding of lignocellulosic and lignocellulosiccontaining fibers, particles or layers to form composite articles is known. Organic di-and polyisocyanates as useful binders for lignocellulose materials have been known for some time and give to particle board products increased stability and mechanical strength; see, for example, 3,428,592; 3,440,189; 3,557,263; 3,636,199; 3,870,665; 3,919,017 and 3,930,110. It is also known in the art that the isocyanate binders are mixed with the wood particles utilized as the base for the particle board. A wood chip or particle and isocyanate binder mixture is then formed into a mat and molded with pressure and temperature to the desired size or shape. Water emulsion polyisocyanate binder systems for use with lignocellulosic particles to prepare particle board are also known. A principal disadvantage of the use of isocyanates in the preparation of particle board is due to their excellent adhesive properties. Thus, isocyanate systems, either the water emulsion or the straight polyisocyanate binders, stick tenaciously to the metal caul plates which are employed to support the wood particles during transporting and the pressing or molding processes. Such poor release of the molded particle board from the caul or mold surface creates difficulty in the cleaning and automatic handling of the cauls. In order to prevent the sticking problem, external release agents have been developed and applied to the caul plates or platens or mat surface as described for example in U. S. Patent No. 4,110,397. Other conventional release agents such as oils, waxes, polishes, silicones and polytetrafluoroethylene have been unsatisfactory as have the specialized urethane release agents including those used in structural foam applications. Another method of overcoming the sticking problem has been to overlay the isocyanate bound lignocellulosic particles with a veneer of wood as shown, for example, in U.S. Patent Nos. 3,390,110; 4,197,219 and 3,919,017, or to use a release paper. These methods have the disadvantage of either adding more cost to the product or of not fully utilizing the superiority of the isocyanate binder. Many of the release agents developed to date have to be applied during every composite production cycle in large quantities to be effective. SUMMARY OF THE INVENTION The present invention provides for the preparation of lignocellulosic composite articles or sheets which comprises shaping in a mold or between mold surfaces a mixture of lignocellulosic particles and a polyisocyanate based binding agent, there being provided on the mold surface or surfaces a terpolymer of a functional polysiloxane, an isocyanate and a hydroxyl substituted monocarboxylic acid or metal salt thereof as a release agent, which release agent may also be admixed with an organopolysiloxane fluid as a diluent. It is an object of the present invention to provide novel compositions which serve as release agents and provide for multiple release of the molded articles. Another object is to provide release agents which are readily applied and adhere to the mold surfaces. A further object is to provide release agents which need only be applied in small amounts. these and other objects and advantages of this invention will become apparent from the description of the invention and from the claims. DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a method for the preparation of lignocellulosic composite molded articles, particularly particle board, by bonding together wood chips or other lignocellulosic or organic material using heat and pressure with an organic polyisocyanate employed as the binding agent and with the application of a film of release agent by dipping, spraying or wiping of terpolymer formed by reacting a functional polysiloxane, an isocyanate and a hydroxyl substituted monocarboxylic acid or metal salt thereof to the mold surface or surfaces. A functional polysiloxane having the formula EMI4.1 of from 1 to 20 and X is a group selected from -CH2OH, -CH(0H3)OH, -COOH, -C(CH3)20H or -OH is reacted with a hydroxyl substituted monocarboxylic acid or a hydroxyl substituted metal salt of the monocarboxylic acid having the formula - CH3-(CH ) -COOZ wherein Z is selected from Hydrogen, Na, Li, Ca, Ba, Cd, 2y K K or Fe which in turn is reacted with an isocyanate having the formula R-NCO wherein R is a group selected EMI4.2 group having from 1 to 6 carbon atoms and y being an integer of from 1 to 20, to form the terpolymer release agent of the present invention. For essentially permanent release or longer production use cycles the mold surface or surfaces with film applied may be heated to between 750C. and 2000C. for from 1 to 5 minutes before. use. The molded lignocellulosic composite such as, for example, particle board or flake board is generally prepared by spraying the particles with the polyisocyanate binder as they are being mixed or agitated in suitable and conventional equipment such as a blender. Suitably, the polyisocyanate binder use levels, based on the oven dried (08 moisture content) lignocellulosic material is from about 1.5 to 12 and preferably 2.5 to 6.5 weight percent. Other materials such as fire retardants may also be added to the particles or sprayed with the binder during the blending or mixing step. After forming a uniform mixture the coated lignocellulosic particles are formed into a loose mat or felt in the desired proportions onto a caul plate of polished aluminium or steel which serves to carry the "cake" into the heated press to consolidate the wood particles into a board of desired thickness. Temperatures of the press are generally between about 1400 and 2200C. and pressures of from about 100 to 600 psi. Pressing times are from about 1 to 10 preferable 3 to 5 minutes Pressing times, temperatures and pressures vary widely depending on the thickness of the board produced, the desired density of the board, the size of the lignocellulosic particles used, and other factors well known in the art. the isocyanate binding agent will generally be an organic polyisocyanate used alone but may also be in admixture with another type of binding agent, e.g. a synthetic resin glue, or in admixture with diluents such as propylene carbonate. The isocyanate may be applied in liquid form, as a solution in an inert. solvent or in the form of an aqueous emulsion. The polyisocyanate component which is used in the present invention in the binder system can be any organic polyisocyanate and include aliphatic, alicyclic and aromatic polyisocyanates that contain at least two isocyanate groups per molecule. Such polyisocyanates include the diisocyanates and higher functionality isocyanates. Mixtures of polyisocyanates may be used which for example are the mixtures of di- and higher functional polyisocyanates produced by phosgenation of aniline-formaldehyde condensate or as described in U.S. Patent Nos. 3,962,302 and 3,919,279. The organic polyisocyanates may be isocyanate-ended prepolymers made by reacting under standard known conditions, an excess of a polyisocyanate with a polyol which on a polyisocyanate to polyol basis may range from about 20:1 to 2:1 and include for example polyethylene glycol, polypropylene glycol, triethylene glycol, etc. as well as glycols or polyglycols partially esterified with carboxylic acids including polyester polyols and polyether polyols. Illustrative of organic polyisocyanates which may be employed include for example, toluene-2,4- and 2,6diisocyanates or mixtures thereof, diphenylmethane diisocyanate, m- and p-phenylene diisocyanates or mixtures thereof, m- and p-diphenylene diisocyanates, polymethylene polyphenyl isocyanates, naphthalene-l, 5-diisocyanate, chlorophenylene diisocyanate,cz,o°-xylene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, 3,3'-ditolylene-4,4-diisocyanate, butylene 1,4-diisocyanate, octylene-l,8-diisocyanate, 1,4-, 1,3- and 1,2-cyclohexylene diisocyanate and in general the polyisocyanates disclosed in U.S. Patent No. 3,577,358, 3,012,008 and 3,097,191. The preferred polyisocyanates are the diphenylmethane diisocyanate 2,4' and 4,4' isomers including the 2,2' isomer and the higher functional polyisocyanate and polymethylene polyphenyl isocyanate mixtures, which may contain from about 20 to 85 weight percent of the diphenylmethane diisocyanate isomers. Typical of the preferred polyisocyanates are those sold commercially as "Rubinate-M" (Rubicon Chemicals, Inc.). In general the organic polyisocyanates will have a molecular weight in the range between about 100 and 10,000. the aqueous organic polyisocyanate or isocyanate-terminated prepolymer emulsions are generally prepared by using any of the techniques known in the art for the preparation of aqueous emulsions or dispersions prior to use of the compositon as binder. In general the polyisocyanate is dispersed in water in the presence of an emulsifying or surface active agent which may be any of the emulsifying agents also known in the art including anidnic and nonionic agents. Preparation of the aqueous emulsions may be carried out as described in U.S. Patent Nos. 3,996,154; 4,143,014 and 4,257,995. The lignocellulosic materials employed to prepare the molded compositions using polyisocyanate binders include wood chips, wood fibers, shavings, sawdust, wood wool, cork bark and the like products from the woodworking industry. Fibers, particles, etc. from other natural products which are lignocellulosic such as straw, flax residues, dried weeds and grasses, nut shells, hulls from cereal crops such as rice and oats and the like may be used. In addition, the lignocellulosic materials may be mixed with inorganic flakes or fibrous material such as glass fibers or wool, mica and asbestos as well as with rubber and plastic materials in particulate form. The lignocellulose may contain a moisture (water) content of up to 25 percent by weight but preferably contains between 4 and 12 percent by weight moisture. The release agents of the present invention consisting of a terpolymer of a functional polysiloxane an isocyanate and a hydroxyl substituted monocarboxylic acid or metal salt thereof may be prepared by reacting, with or without an inert solvent such as aromatic or aliphatic hydrocarbons, e.g., toluene, xylene, benzene, heptane, hexane, etc. to control and maintain solution viscosity, at a temperature of from about 500C. to 1500C. and preferably 900C. to 1100C. an excess of a silanol terminated functional polysiloxane having the formula EMI8.1 a group selected from -CH2OH, -CH(CH3)OH, -^OOH,-C(CH3)20H, or -OH, with a hydroxyl substituted monocarboxylic acid or hydroxyl substituted metal salt of the monocarboxylic acid having the formula CH3-(CH2)y-COOZ wherein y is an integer of from 5 to 24 and Z is a group selected from hydrogen, Na, Li, Ca, Ba, Cd, Mg, K or Fe thus forming a copolymeric reaction product which is then reacted at a temperature of from about 50 C. to 1500.C. preferably 900C. to 1100C. with no more than a stoichiometric amount of an isocyanate having the formula R-NCO wherein R is a group selected from CH2(CH2)yNCO# CH3-(CH2)yt EMI8.2 R1 being hydrogen or an alkyl group having from 1 to 6 carbon atoms and y being an integer of from 1 to 20 to form the terpolymer. The condensation reaction to form the terpolymer release agent may be considered completed when no free NCO can be detected by known analytical methods such as Infra Red. The reaction with the isocyanate and copolymer reaction product inlay be carried out in the presence of from 0 to 50 weight percent inert aqueous free (dry) solvents containing no hydroxyl groups such as the aromatic or aliphatic hydrocarbons, e.g. toluene, xylene, heptane. hexane etc. to maintain and control solution viscosity. 5 to 50% solids solutions may be prepared by the condensation process but are preferably prepared and applied as 10 to 20% solids solutions. As indicated herein above organopolysiloxane fluids may be employed along with the terpolymer release agents as a diluent and are used in amounts of from 0 to 25 weight percent, preferably from 10 to 20 weight percent based on the total terpolymer release agent-organopolysiloxane fluid mixture. The organopolysiloxane fluids suitable for use in this invention are generally alkylterminated polysiloxane fluids having from 1 to 18 carbon atoms bonded to the silicon atom. Examples of suitable organopolysiloxane fluids are those having alkyl radicals such as methyl, ethyl, propyl, butyl, hexyl, oxtyl, decyl, dedecyl, tetradecyl, hexadecyl, octadecyl and the like; aryl radicals such as phenyl and naphthyl and mixtures thereof. Generally, it is preferred that the organopolysiloxane be free of terminal-hydroxyl groups; however, a small number of terminal-hydroxyl groups will not materially affect the mold release composition The organopolysiloxane may have a minor proportion of molecules with only one hydroxyl group or there may be a small number of molecules present carryitlg in excess Qf two hydroxyl groups. However, as mentioned previously. it is preferred that the organopolysiloxane be substantially free of hydroxyl groups. In general, the polysiloxane fluids should have a molecular weight of between about 3,000 and 90,000 which is equivalent to a viscosity of between about 50 and 100,000 centipoises, preferably from about 100 to 5,000 centipoises. Optimuin results have been obtained in the lower portion of these ranges such as from about 200 to 500 centipoises. In addition, it is possible to combine high and low viscosity fluics to form a Flaid having the desired viscosity range The organopolysiloxane fluids used in accordance with this invention may be represented by the formula EMI10.1 wherein R,R' and R" which may be thm same or different represent organic groups having from 1 to 18 carbon atoms, preferably alkyl groups having from 1 to 4 carbon atoms, and y has a value of from 80 to about 150,000. The novel mold release agents of the instant invention, whether the polysiloxane-monoc.#rboxylic acid or salt-isocyanate terpolymer alone o the terpolymer admixed with an organopolysiloxane fluid, may he employed in a liquid organic solvent which would preferably he sufficiently volatile to vaporize during t;sfs application process. Preferred solvents include toluene, xylene, benzene, naphtha type solvents, higher C4 to C10 alcohols such as isobutanol and hydrocarbon solvents such as perchloroethylene. The functional polysiloxane-monocarboxylic acid or salt-isocyanate terpolymer release agent may be applied to the mold surfaces as a concentrated or dilute solution or as a dispersion. It is preferred that the release agent composition be dissolved in a volatile organic solvent such as a mixture of toluene and isobutanol and then sprayed, wiped or brushed onto the mold surfaces in the form of a thin film. This may best be obtained by rubbing the mold surface or surfaces with a swab saturated with a solution of the release composition. However, when practical, the mold surfaces may be sprayed with the composition to form a thin film thereon. Once the release composition has been applied to the mold surfaces, it may be used immediately. However, it is preferred that the coating be dried especially when an organic solvent has been used. More preferably, as indicated hereinbefore the coated mold surfaces are heated to between about 750 to 2000C. for from 1 to 5 minutes to fill all pores and openings and to provide for an essentially permanent release or longer production use cycles. The following examples are provided to illustrate the invention in accordance with the principles of this invention, including examples of a comparative nature, but are not to he construed as limiting the invention in any way except as indicated by the appended claims. EXAMPLE 1 580 grams of pine wood chips dried to a moisture content of 6 percent were placed in an open tumbler-mixer. During tumbling 16 grams of a diphenylmethane diisocyanate-polymethylene polyphenylisocyanate (PMDI) mixture having a 46.5 percent diphenylmethane diisocyanate content as a binder was sprayed evenly onto the wood chips by an air pressurized system. Two new aluminium caul plates 12" x 12" x 3/16" were wiped with a cloth saturated with a terpolymer release agent mixture of 10 parts by weight of a polymerization reaction product of a silanol (-CH2OH) terminated polydimethyl siloxane, having a molecular weight of 28,000, 12-hydroxy stearic acid, and a diphenylmethane diisocyanate-polymethylene polyphenyl isocyanate (PMDI) mixture having a 46.5% diphenylmethane diisocyanate content and 90 parts by weight toluene. The terpolymer was prepared by charging 50 grams of silanol(-CH2OH) terminated polydimethyl siloxane(MW 28,000) and 6 grams 12-hydroxy stearic acid into a 250ml reaction flask in 50% by weight toluene. The reaction was run for 3 1/2 hours at 900C. in nitrogen with steady stirring. The reaction was cooled and .23 grams of diphenylmethane diisocyanate-polymethylene polyphenyl isocyanate (PMDI) having 46.5% diphenylmethane diisocyanate was charged into the reaction flask. The complete mixture of materials was reacted for 4 additional hours at 1000C. in nitrogen under steady stirring at which time no free NCO could be detected by infra red analysis. Toluene was added to make a solution of 10% solids. The polyisocyanate coated wood chips were then preformed in a box 10.5 inches square and 12 inches high whic#'wa's"" v supported by one of the terpolymer release agent coated caul plates and prepressed to form a thick mat. The box was then taken out and the second coated caul plate placed on top of the mat. The whole assembly was subjected to a temperature of 1900C., pressed to stops at a thickness of 13mm and held for 4 minutes and the pressure released. The lignocellulosic (wood chip board) composite was easily released from the caul plates. The board making procedure as above was repeated four additional times using the same originally coated caul plates with easy release of the composite. EXAMPLE 2 The procedure of Example 1 was repeated except that the aluminum caul plates wiped with the silanol terminated polydimethyl siloxane-12 hydroxy stearic acidisocyanate terpolymer release agent mixture was heated at 176 C. for 3 minutes prior to use. Six repeated cycles of board preparation and release at 1900C. were recorded. EXAMPLES 3 to 8 Various terpolymers of silanol terminated polydimethyl siloxanes, molecular weight 28,000, with a monocarboxylic acid or metal salt thereof were prepared by reacting 1 part by weight of the silanol and 1 part by weight of the acid or metal salt in a 250. ml reaction flask with 50% by weight toluene. The siloxane-acid reaction was run for four hours at 950C. in nitrogen with stirring, cooled and then reacted with 1 part by weight of diphenylmethane diisocyanate-polymethylene polyisocyanate (PMDI) having 46.5% diphenyl methane diisocyanate which reaction was run for 4 hours at 1000C. in nitrogen with stirring until no free NCO could be detected by infra red analysis. Toluene was added to provide a 10% solids solution. The procedure of Example 1 was repeated to produce particle board using the release agents and giving the release cycles as indicated below Terpolymer Release Cycles Example No. Release Agent at 1900C. 3 Silanol(-CH2OH) terminated Polydimethyl Siloxane and 12-Hydroxy Calcium Stearate 4 with PMDI 4 Silanol (-CH2OR) terminated Polydimethyl Siloxane and 12-Rydroxy Iron Stearate 5 with PMDI 5 Carhinal (-COH) terminated Polydimethyl Siloxane and 2-Hydroxy Potassium.Oleate - 6 with PMDI 6 Carboxy (-COOH) terminated Polydimethyl Siloxane and 12-flydroxy Stearic Acid 7 with PMDI 7 Silanol (-CH2OH) terminated Polydimethyl Siloxane with 2-Hydroxy Capric (decanoic) Acid and phenylisocyanate 5 8 Silanol (-CH2OH) terminated Polydimethyl Siloxane with 12-Hydroxy Palmitic (hexadecanoic) and hexamethylene diisocyanate 6 EXAMPLE 9 The procedure of Example 2 was repeated employing 85% of the terpolymer of Example 1 mixed with 158 polysiloxane fluid and diluted to a 108 solids solution with toluene. Six repeated cycles of particle board preparation and release at 1900C. were recorded. EXAMPLE 10 The procedure of Example 2 was repeated employing an 80;20 mixture of the terpolymer of Example 5 and polydimethyl siloxane fluid diluted to 108 in a 50:50 mixture of toluene and isobutanol. Five repeated cycles of particle board preparation and release at 1900C. were recorded. EXAMPLE 11 CONTROL Example 1 was repeated except that no release agent was applied to the caul plates. The pressed lignocellulosic composite could not be released even after cooling down. EXAMPLE 12 CONTROL Examples 1 and 2 were repeated except that the caul plates in three composite preparations were wiped with a 15% solution of zinc stearate, aluminum stearate and lithium stearate in isobutanol. Only one cycle of release was recorded with each when hot (190 C.).

Claims: CLAIMS 1. A process for the preparation of lignocellulosic composite molded articles wherein lignocellulosic particles are contacted with an organic polyisocyanate-based binder composition and the treated particles are subsequently formed into molded articles by the application of heat and pressure, characterised in that a film coating of a terpolymer which is formed by reacting a functional polysiloxane, a hydroxyl substituted monocarboxylic acid or metal salt thereof and an isocyanate is provided on the mold surface or surfaces to facilitate release of the lignocellulosic molded article, said function polysiloxane having the formula: : EMI16.1 wherein n is an integer of from 5 to 30, m is an integer of from 1 to 20 and X is a group selected from -CH2OH, -CH(CH3)OH, -C(CH3)20H, -COOH or -OH, said monocarboxylic acid or metal salt thereof having the formula CH3-(CH2) -COOZ wherein y is an integer of from 5 to 24 and Z is a group selected from hydrogen, Na, Li, Ca, Ba, Cd, Mg, K and Fe, and said isocyanate having the formula R-NCO wherein R is a EMI16.2 being hydrogen or an alkyl group having from 1 to 6 carbon atoms and y being an integer of from 1 to 20. 2. A process according to claim 1 wherein the lignocellulosic composite article is particle board. 3. A process according to claim 1 or claim 2 wherein the lignocellulosic composite is compressed between metal platens at a temperature of from about 400C to 2200C and a pressure of from about 100 psi and 600 psi for a period of from 1 to 10 minutes, preferably 3 to 5 minutes. 4. A process according to any one of claims 1 to 3 wherein the coated mold surface or surfaces are heated at a temperature of from about 750C to 2000C for a period of from about 1 to 5 minutes prior to preparation of lignocellulosic composite molded articles. 5. A process according to any one of claims 1 to 4 wherein the organic polyisocyanate binder is selected from diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanates containing from about 20 to 85% by weight diphenylmethane diisocyanate. 6. A process according to any one of claims 1 to 5 wherein the function polysiloxane is terminated by a group selected from -CH20H, -C(CH3)20H and -COOH. 7. A process according to any one of claims 1 to 6 wherein the hydroxyl substituted monocarboxylic acid of the terpolymer is 12-hydroxy stearic acid. 8. A process according to any one of claims 1 to 7 wherein the isocyanate of the terpolymer is selected from hexamethylene diisocyanate, phenylisocyanate and polymethylene polyphenyl polyisocyanates containing from 20 to 85% by weight diphenylmethane diisocyanate. 9. A process according to any one of claims 1 to 8 wherein the functional polysiloxanes, hydroxyl substituted monocarboxylic acid or metal salt thereof and isocyanate are applied in admixture with a solvent which is preferably selected from toulene, isobutanol and mixtures thereof. 10. A process according to any one of claims 1 to 9 wherein from 0 to 25 weight percent and preferably between 10 and 20 weight percent, organopolysiloxane fluids, based on the combined weight of the terpolymer and said fluids, is added as diluent. 11. A lignocellulosic composite molded article e.g. a composition board product, prepared by the process claimed in any one of claims 1 to 10. 12. As a new composition of matter, a terpolymer as specified in any one of claims 1, 6, 7 and 8.

Inventors: GAUL, JAMES M., NGUYEN, TINH
Applicants: ARCO CHEMICAL TECHNOLOGY INC.
Application year: 1984
Main classification: B29C33
IPC codes: B29C33, C08G18