Adhesive compositions, reaction systems and methods of producing lignocellulose composites
SUBSTANCE: adhesive composition contains a polyfunctional isocyanate, polyether polyol and a catalyst. The catalyst consists of at least one organic compound of iron and at least one chelating ligand. The multicomponent adhesive composition is prepared in form of at least two inter-reacting chemical components. One of the at least two inter-reacting chemical components contains a polyfunctional isocyanate and a catalyst, and the other contains polyether polyol. The multicomponent adhesive composition is used to produce articles from bound lignocellulose composite based on a lignocellulose substrate, especially for making oriented fibre panels.
EFFECT: invention enables to obtain articles using filler with high moisture content, which are structured at low pressing temperatures without reducing efficiency of the press.
4 tbl, 1 ex, 17 cl
The SCOPE of the INVENTION
The description refers to adhesives, reactive systems and methods for use in the manufacture of lignocellulosic composites.
BACKGROUND of INVENTION
Production being formed by extrusion of composites from a mixture of wood shavings (sawdust) or fibers and polyisocyanate binders well known. Isocyanate binders are an excellent bonding agents for shavings (sawdust) or fibers, but they require the use of high temperatures during compaction during production of composite panels (plates) of these lignocellulosic powder substrates.
Often the desired temperature pressing over 400°F, often as high as 430°F or even higher, in order to achieve effective curing of the binder in a reasonable period of time. There is a compromise value between the temperature of the pressing time and in the press. Lower temperature extrusion usually result in a longer residence time in the press. Longer time spent in the press undesirable for the industry because they reduce the productivity in the production process. High temperature pressing require more energy and are often the reason for the selection of undesirable quantities of VOCS (VOC; volatile organic connection of the clusters) from the substrate during pressing. In addition, high temperatures often cause thermal damage to the composite panels (plates) and, in some cases, even the fire in the press. The need for a high degree of heat has a tendency to bring the moisture content in the final product (panel Board) to undesirable low levels.
Types of polyisocyanate binders used in practice in the industry, are almost without exception isocyanates series DHS, usually polymeric MDI (which belong to different mixtures of diphenylmethanediisocyanate and heavier polymethylenepolyphenylisocyanate the oligomers). These polyisocyanate binders, most are strong binders phenol-formaldehyde (FF; PF) type in relation to the quality of the panels (plates). Lignocellulosic composites produced using binders DHS, are typically more resistant to moisture damage than similar panels (plates)manufactured using FF resin. An additional advantage of MDI binders, which made them highly attractive for the production of SURFACE (OSB; plate with oriented fiber), is a large permissible moisture content of the substrate. MDI binder, as opposed to FF resins, can often be used with a wood substrates, kotoryi.kot higher moisture content. FF resins require a very high temperature pressing at practically acceptable for the industry terms of presence in the media. Widely used form DHS Poliziano works best with wood substrates (chips, sawdust and/or fibers, often referred to in industry as "fillers"), which were pre-dried to a moisture content in the range of from about 2 to 6% by weight. This humidity still requires some pre-drying filler, though usually not as large as for FF binders. By pre-drying uses large amounts of energy and requires an additional step in the manufacturing process. It also requires additional equipment and creates a new kind of danger - fire kiln. It would be highly desirable for the practice in the industry to completely eliminate preliminary drying or, at least, to obtain a further reduction in the volume of pre-drying.
Therefore, in the industry of wood composites there is a strong demand, especially in the production of pressed powder wood composites, such as the production of panels with oriented fibers (DOV), in binding substances, which can be used at higher moisture content of the fillers, and which will be structured when Bo is its low temperature extrusion without reducing the productivity of the press. It would be desirable to apply temperature pressing of less than 400°F, preferably, 350°F or below, without increasing term presence in the press. It would also be desirable to use a filler with a moisture content of more than 6% by weight. The binder that can successfully meet all of these needs, has the potential to significantly reduce the cost of the product by reducing energy consumption. Additional benefits include improved product quality, reduced emissions, and improved security for plants.
SUMMARY of the INVENTION
One of the embodiments of the invention, which meets the needs stated above, is a reaction system for the production of particles of a lignocellulosic composite. The reaction system contains a multi-component adhesive composition and the lignocellulosic substrate. Lignocellulosic substrate preferably includes multiple binders for lignocellulose. More preferably, the lignocellulosic substrate consists essentially of a mass of lignocellulosic particles. Multi-component adhesive composition contains at least two vzaimorezerviruemym component that it is advisable to apply with lignocellulosic substrate as separate threads. Multi-component glue is the first composition comprises, at least, polyfunctional isocyanate, a hydrophilic polyol and a catalyst. The catalyst preferably contains at least one ORGANOMETALLIC compound of a transition metal.
Preferred ORGANOMETALLIC compounds of transition metals are those that can be used in a mixture with a polyfunctional isocyanate. To provide sufficient compatibility with isocyanates at room temperature is highly desirable that the catalyst is essentially free of compounds of alkali metals and alkaline earth metals. In addition, it is preferable that the catalyst is essentially free of compounds of other metals that can cause significant interactions MDI in environmental conditions, in particular, compounds of tin. A highly preferred class of catalysts are organic compounds of iron, especially iron compounds with chelating ligands. A preferred group of hydrophilic polyols are the polyether polyols based solely or predominantly of ethylene oxide, and oxyethylene segments constitute more than 50% of the weight of the polyol. Polyfunctional isocyanate, preferably, includes one or more isocyanates in a series of MDI. Preferred polyfunctional isocyanate is, beings who, one or more representatives of a series of DHS and, more preferably, is a mixture of one or more of diphenylmethanediisocyanate isomers with one or more of the high-molecular oligomers series MDI (polymethylenepolyphenylisocyanate).
Another embodiment that meets the needs presented above is a method for the production of lignocellulosic composites. This method at least comprises the following stages:
a) obtaining a lignocellulosic substrate. Lignocellulosic substrate, preferably, contains a variety of lignocellulosic bindable substances. More preferably, the lignocellulosic substrate consists essentially of a mass of lignocellulosic particles;
b) obtaining multi-component adhesive compositions containing at least a polyfunctional isocyanate, a hydrophilic polyol and a catalyst. Multi-component adhesive composition at least comprises two vzaimorezerviruemym thread, but can, if desired, include more than two threads. The preferred composition the main ingredients of a multi-component adhesive compositions (polyfunctional isocyanate, a hydrophilic polyol and catalyst) presents those discussed above;
c) application of separate, interacting components of a multicomponent adhesive composition for lignocellulosic su the strata, preferably in the form of independent threads without any prior mixing of the components in quantities suitable for receiving articles from the associated lignocellulosic composite;
(d) molding and extrusion processed adhesive composition of lignocellulosic substrate under conditions suitable for structuring (hardening) of the binder and receipt of product from the associated lignocellulose composite;
e) removing from the form of the product of the associated lignocellulose.
In a highly preferred embodiment of this method, the catalyst is first mixed with the polyfunctional isocyanate and applied to the substrate in the form of a single jet stream. The hydrophilic polyol is applied to the substrate in the form of the second jet stream. When the preferred examples of this method of multi-component adhesive composition is applied to the lignocellulosic substrate in the form of two vzaimorezerviruemym flows of chemical compounds.
Another embodiment includes binders for use in the manufacture of lignocellulosic composites. Multi-component adhesive composition includes at least two vzaimorezerviruemym component, which are preferably applied to the lignocellulosic substrate as separate threads. Multi-component adhesive composition includes polyfunction the local isocyanate, hydrophilic polyol and a catalyst. The catalyst preferably includes at least one ORGANOMETALLIC compound of a transition metal. Preferred ORGANOMETALLIC compounds of the transition metal are those that can be used in a mixture with a polyfunctional isocyanate. To provide sufficient compatibility isocyanate at room temperature is highly desirable that the catalyst is essentially free of compounds of alkali or alkaline earth metals. In addition, it is preferable that the catalyst is essentially free of compounds of other metals that can cause significant side interaction MDI in environmental conditions, especially compounds of tin. A highly preferred class of catalysts are organic compounds of iron, in particular of iron compounds with chelating ligands. A preferred group of hydrophilic polyols are the polyether polyols based solely or predominantly of ethylene oxide, and oxyethylene segments constitute more than 50% by weight of the polyol. Preferably, polyfunctional isocyanates include one or more isocyanates in a series of MDI. Preferred polyfunctional isocyanate consists essentially of one or more representatives from the series MDI and bol is E. preferably, consists of a mixture of one or more of diphenylmethanediisocyanate isomers with one or more of the high molecular weight oligomers of a series of MDI (polymethylenepolyphenylisocyanate).
Unexpected, and unexpectedly it was found that data binders, reactive systems and processes facilitate the production of moldable lignocellulosic composites, especially composites formed from the mass of powder lignocellulosic filler, low temperature pressing without increasing term presence in the press. In addition, it was discovered, quite unexpected that these binders, reactive systems and processes facilitate the production of lignocellulosic composites of the filler with a high moisture content. You can use a filler having a moisture content greater than 6% by weight, and the pressing can be performed at temperatures of pressing 350°F or below. Data binders, reactive systems and processes are particularly suitable for the production of plates with oriented fiber (DOV; OSB).
Described binders for use in the manufacture of lignocellulosic composites. The adhesive composition includes two components that interact preferably be applied to the lignocellulosic substrate as separate threads. Megacomponents what I adhesive composition comprises a polyfunctional isocyanate, hydrophilic polyol and a catalyst. The catalyst preferably contains at least one ORGANOMETALLIC compound of a transition metal. Preferred ORGANOMETALLIC compounds of the transition metal is acceptable for use in a mixture with a polyfunctional isocyanate. To provide sufficient compatibility with the isocyanate at room temperature, it is extremely desirable that the catalyst is essentially free of compounds of alkali or alkaline earth metals. In addition, it is preferable that the catalyst is essentially free of compounds of other metals that can cause significant side interaction MDI in environmental conditions, especially compounds of tin. A highly preferred class of catalysts are organic compounds of iron, in particular of iron compounds with chelating ligands. A preferred group of hydrophilic polyols are the polyether polyols based solely or predominantly of ethylene oxide, and oxyethylene segments constitute more than 50% by weight of the polyol. Preferably, polyfunctional isocyanates include one or more isocyanates in a series of MDI. Preferred polyfunctional isocyanate consists essentially of one or more representatives of a series of DHS and, more predpochtitel is about, consists of a mixture of one or more of diphenylmethanediisocyanate isomers with one or more of the high molecular weight oligomers of a series of MDI (polymethylenepolyphenylisocyanate).
The reaction system to obtain adhesive related products from lignocellulosic composite is described. This reaction system includes a multi-component adhesive composition and the lignocellulosic substatially to lignocellulosic substrate consisted of many lignocellulosic particles bonded material. More preferably, when the lignocellulosic substrate consists essentially of a mass of lignocellulosic particles, such as wood shavings (sawdust and/or wood fibers. These particles are small compared with the end generated by pressing the product from lignocellulosic composite, typically having a maximum length in any direction less than six inches. In a particularly preferred application, such as the production of panels with oriented fibers (DOV), the substrate consists essentially of a mass of flat wood chips, each of which has a maximum length of less than six inches, width less than three inches and a thickness of about half an inch or less. Wood chips usually have variable size and shape.
Multi-component adhesive composition, as a minimum, includes the VA vzaimorezerviruemym component, which are preferably applied to the lignocellulosic substrate in the form of separate streams (separate chemical components). Multi-component adhesive composition comprises a polyfunctional isocyanate, a hydrophilic polyol and a catalyst.
Polyfunctional isocyanate is, most typically, the aromatic polyisocyanate. Aromatic polyisocyanates are the most widely used as binders in the manufacture of moldable lignocellulosic composites are polyisocyanates series DHS, most typically, polymeric MDI. Polymeric MDI is a mixture of several diphenyldiisocyanate isomers and polymethylenepolyphenylisocyanate with high functionality, making up more than 2. These isocyanate mixtures usually contain more than half, by weight, varieties with high functionality. Other diisocyanates present in the polymeric MDI, usually dominated by 4,4'-MDI isomer and smaller amounts of 2,4'-isomer, and there are traces of the 2,2'-isomer. Polymeric MDI is a product of vosganian complex mixture of aniline-formaldehyde condensates. It usually contains from 30 to 34% by weight of isocyanate (-NCO) groups and has an average functionality isocyanate groups from 2.6 to 3.0.
However, in the scope of this specification includes the use of any polifunctional the aqueous organic isocyanate binder. Non-limiting examples of other types of polyfunctional isocyanates that can be used include one or more of the representatives selected from the group consisting of aliphatic, alifaticheskih, aromatic and heterocyclic polyisocyanates, having an average functionality isocyanate (-NCO)groups of 2 or more and the concentration of organically related isocyanate groups of from about 1% by weight to about 60% by weight. A number of polyisocyanates that can be used includes prepolymers, pseudoparalysis and other modified variants of Monomeric polyisocyanates, known to specialists in this field, which contain free isocyanate reactive organic group. Preferred polyfunctional isocyanates are liquid at 25°C.; viscosity at 25°C less than 10,000 centipoise, more preferably less than 5,000 centipoise; and have a concentration of free organically related isocyanate groups from 10 up to 33.6% by weight. The most preferred polyisocyanates are isocyanate-series MDI. Preferred isocyanates series MDI include polymeric MDI and prepolymers, variants or derivatives, which are known to experts in this field. Especially preferred group of isocyanates series MDI are isocyanates, which are essentially free from f is polimerov, containing less than 1% by weight, more preferably less than 0.1% by weight, and optimally, 0% terpolymerization species. Representatives of this particularly preferred group of isocyanates series DHS have concentrations of free organically related isocyanate groups from 31% to 32% by weight, the average functionality of isocyanate groups (NCO) from 2.6 to 2.9 and a viscosity at 25°C. of less than 1000 centipoise.
Multi-component adhesive composition also contains at least one hydrophilic polyol. The term "polyol" means a polyfunctional organic compound with active hydrogen. Hydrophilic polyol most preferably is an organic polyol, and present isocyanatoacetate functional group with active hydrogen consists, essentially, of primary and/or secondary organically linked hydroxyl groups; although you can use connections to other isocyanatomethyl functional groups. In preferred embodiments of the prevailing isocyanatoacetate group with an active hydrogen present in the hydrophilic structure of organic polyols on a molar basis, are organically bound primary and/or secondary hydroxyl groups. In a particularly preferred embodiment only isocyanatomethyl groups with active is hydrogen, present in the hydrophilic structure of hydrophilic polyols, are organically related primary and/or secondary hydrophilic group. Primary organically linked hydroxyl groups are most preferred. In one embodiments the molar ratio of primary organically linked hydroxyl groups to secondary organically bound hydroxyl groups present in the hydrophilic polyol as one structure is more than 1:1, more preferably more than 2:1, more preferably greater than 4:1, and most preferably, more than 9:1.
Non-limiting examples of suitable alternative Sozialforschung functional groups with active hydrogen, which can be used in the structure of the hydrophilic polyol, or in addition to, or instead of the primary and/or secondary organically linked hydroxyl groups include one or more members selected from the group consisting of primary and secondary organically linked amino groups. Optionally, you can use a combination of different polyols. The polyol contains two or more Sozialforschung groups with active hydrogen in the molecule. Hydrophilic polyol has a certain degree of compatibility with water. Preferred hydrophilic polyols are mixed with water in all proportions. Especially prepact the positive group of hydrophilic polyols are aliphatic polyether polyols, which contain ethylenoxide (oxyethylene) elements. More preferred hydrophilic polyether polyols of this group have the content oxyethylene groups of more than 50% by weight, more preferably more than 70% by weight. Preferred hydrophilic polyol has a functionality isocyanatoacetate group with an active hydrogen on an average number of from 2 to 10, preferably from 2 to 6, more preferably from 3 to 5, and more preferably from 3 to 4. Thiols are the most preferred. If you prefer, you can use a mixture of different hydrophilic polyols. If you prefer, you can use a separate polyols, which contain a combination of different types Sozialforschung groups with active hydrogen, such as hydroxyl groups and primary and/or secondary amino group in the same molecule. The overall functionality of these polyols with mixed functionality, as it is clear, is the sum of the individual Sozialforschung functionalities groups with active hydrogen.
Organic hydrophilic(e) polyol(s) may optionally be used in combination with one or more of the monofunctional species of organic compounds with active hydrogen, such as monopoly or monoamines, which do not contain other Sozialforschung groups with active hydrogen, and the like. Prisutstvie the e these kinds of monofunctional organic compounds with active hydrogen should preferably be eliminated or minimized.
It is desirable that the molecular weight (average number) hydrophilic organic polyol was between about 300 and 10,000, but more preferably, between 400 and 6000, more preferably between 600 and 4000, more preferably between 700 and 2000, and most preferably from 800 to 1500. The preferred polyether polyols are usually obtained by methods well known to specialists in this field, such as the connection of alkalisation one or more species with one or a combination of polyfunctional initiators. The most preferred alkalization is ethylene oxide, but you can use other types of alkalisation (preferably in small amounts), together with ethylene oxide. Non-limiting examples of arbitrary alkalisation include propylene oxide, butylenes, oxides of aliphatic alpha-olefins, aromatic oxides, alpha-olefins, such as styrene oxide and combinations of these compounds. Non-limiting examples of suitable polyfunctional initiators include ethylene glycol, water, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol, 1,3-butanediol, glycerol, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, glucose, sucrose, triethanolamine, triisopropanolamine, ethylene diamine, ethanolamine, any isomers tolualdehyde, 4,4'-diaminodiphenylmethane, 2,4'-Diamanti Eilean, bisphenol-A, any of the isomers of dihydroxybenzene and combinations of these compounds. Water-soluble initiators are preferred, and is completely miscible with water initiators even more preferred. Especially preferred initiator is glycerol.
Non-limiting examples of suitable hydrophilic polyether polyols include ethyleneoxide adducts of glycerol, ethyleneoxide adducts of trimethylolpropane, ethylenoxide and propyleneoxide adducts of glycerol, and the content of oxyethylene is more than - 50% by weight, ethylenoxide and propyleneoxide adducts of trimethylolpropane, and the content of oxyethylene is more than 50% by weight, ethylenoxide and butylaniline adducts of glycerol and/or trimethylolpropane, and the content of oxyethylene is more than 50% by weight, and mixtures of these compounds. If you use more than one accelerated, the distribution may be random, block or represented by their combination. You can use a mixture of different polyether polyols, but highly preferably, the total content of oxyethylene these mixtures was more than 50% by weight, preferably more than 70% by weight or more by weight of this mixture.
Multi-component adhesive composition according to this invention can be optionally applied to the substrate in combination with a known binder in the company not isocyanate type, but more typically, when put only this substraction total load binders (including all components of multi-component adhesive composition according to this invention, plus any binders are not isocyanate type, which can be used are in the range of from about 1 to about 6% by weight from the lignocellulosic substrate, more typically, from about 1.5 to about 4%.
Multi-component adhesive composition further contains a catalyst. The catalyst preferably contains at least one ORGANOMETALLIC compound of a transition metal. In the preferred embodiment, the catalyst consists essentially of one or more of the ORGANOMETALLIC compounds of transition metals. Preferred ORGANOMETALLIC transition metal compounds contain one or more of the metals selected from the group consisting of metals of groups IVB, VB, VIB, VIIB and VIIIB of the Periodic table of elements. A more preferred group of ORGANOMETALLIC compounds of transition metals suitable for use as catalysts in this reaction system contains one or more of the metals selected from the group consisting of metals of group VIIIB of the Periodic table. Particularly preferred ORGANOMETALLIC compounds of iron. The catalysts of the met is reorganises of transition metal compounds preferably contain one or more of the chelating ligands. Non-limiting examples of chelating ligands include acetylacetone, alkalemia or akrilovye acetoacetate esters, gluconate, cyclopentadienyl, and combinations thereof. Acetoacetone (ASAS) and acetoacetate are examples of preferred chelating ligands. One group of particularly preferred ORGANOMETALLIC catalysts suitable for use in the reaction systems of this invention are the catalysts described in the following U.S. patents, which are incorporated here by reference: US 5587414, US 6288200, US 6908875, US 6750310, US 6288255 and US 6762314.
The most preferred ORGANOMETALLIC compounds of transition metals are those that can be used in a mixture with a polyfunctional isocyanate. To ensure adequate compatibility of the catalyst with the isocyanate at ambient temperatures and to avoid instability due to unwanted side reactions of the isocyanate before use or during the deposition process, it is extremely desirable that the catalyst is essentially free of compounds of alkali or alkaline earth metals. In addition, it is preferable that the catalyst is essentially free of compounds of other metals that can cause significant personal interaction of polyisocyanates in environmental conditions, especially the of soedinenii tin. Under "significant private interactions" refers to the reaction of isocyanate groups with other isocyanate groups and/or other chemical groups present in the polyfunctional isocyanate composition that is sufficient to create a nuisance to use polyfunctional isocyanate or storage conditions ambient temperature (room temperature) in a dry air environment for at least 24 hours, preferably at least 1 week, more preferably at least 2 weeks, more preferably for at least 4 weeks, more preferably for at least 60 days and most preferably for at least 180 days. It is desirable that the content of free isocyanate (-NCO) in the polyfunctional isocyanate, expressed in percentage by weight, shall not vary more than one percent during storage or use before application to the substrate. By "essentially does not contain", "essentially free", "being deprived" means that the total catalyst composition contains less than 10% by weight in General (relative to the total weight of the catalyst composition) of all these destabilizing compounds, more preferably, less than 1%, more preferably less than 0.5%, more preferably less than 0.1%, and most is preferable, less than 0.01% by weight. Ideally, there should be detectable quantities of these compounds present in the catalyst composition.
If you prefer, you can use a combination of different catalysts from ORGANOMETALLIC compounds of transition metals. The preferred catalysts from ORGANOMETALLIC compounds of transition metals can, if desired, be used in combination with conventional urethane catalysts such as tertiary amines. When the catalyst is intended for use in direct contact with the polyfunctional isocyanate species present tertiary amines, if they are present, and their levels should be adjusted to ensure sufficient stability of the isocyanate, as described above. In preferred embodiments of the catalysts from ORGANOMETALLIC compounds of transition metals are the only catalysts used in multicomponent systems binders.
The catalyst or catalysts can be used in the reaction system in the form of a single thread or multiple threads can be used in combination with one or more other components of a multicomponent adhesive compositions or any combination of these alternatives. In preferred embodiments, the reaction with the system, at least one of the ORGANOMETALLIC transition metal compounds are mixed with the polyfunctional isocyanate. In a broader sense, though, in General, less preferably, be used, if desired, such additional catalysts as tertiary amines in combination with hydrophilic polyol as separate streams, or any combination of them.
In more preferred embodiments the reaction system of multi-component adhesive composition consists of only two vzaimorezerviruemym components: flow polyfunctional isocyanate containing at least one catalyst of the ORGANOMETALLIC compounds of transition metals and a second stream comprising at least one hydrophilic polyol. Hydrophilic polyol, preferably, is the main ingredient by weight in the second thread. Polyfunctional isocyanate, preferably, is the main ingredient by weight in the first stream.
Multi-component adhesive composition may optionally also contain other ingredients in addition to the polyfunctional isocyanate, a catalyst and a hydrophilic polyol. You can use other types known optional additives. Non-limiting examples of optional additives that can be used include flame retardants, such as Tris-(chloropropyl)phosphate(DPF), triarylphosphine, such as triphenyl, melamine, melamine resin and graphite; pigments, dyes; antioxidants, such as triarylphosphite (i.e. triphenylphosphite) and shielded phenols (i.e. BGA, OSH, etc); light stabilizers; a blowing means; inorganic fillers, organic fillers (different from the lignocellulosic material used in the substrate); a surge of smoke; paraffin GAC (liquid and low-melting hydrocarbon waxes); antistatic tools; internal tools for liberation from forms such as soap, dispersible solid waxes, silicones and fatty acids; inert liquid diluents, especially non-volatile diluents such as triglyceride oils (soybean oil, linseed oil and the like); solvents, especially relatively nonvolatile solvents such as propylene carbonate; biocides, such as boric acid; combinations of these substances, and the like. Methods of using these and other known optional additives, and specific examples and their corresponding number will be understandable to experts in this field. These optional additives can, if desired, be used in whole or in part in the form of separate streams of components. In preferred embodiments of the optional ingredients, when they are used, entering the formula used in a two-line system, discussed above.
Lignocellulosic raw material, usually in the form of fine shavings, fibers, particles, or mixtures thereof, pretreated components of multi-component adhesive compositions and tilt the mixer to ensure adequate distribution of the adhesive composition on the raw substrate. Processed adhesive composition of lignocellulosic raw material is then pre-formed into a very loose weight before pressing. The relative amounts of the various ingredients in the multi-component adhesive composition, which is applied to the substrate can vary significantly. In most embodiments the ratio of the number of isocyanate (-NCO) groups to the total number isocentricity groups with active hydrogen in the multi-component adhesive composition is between 1:40 and 40:1. In preferred embodiments the ratio of equivalents vzaimozachetnykh functional groups is between 1:20 and 20:1, more preferably between 1:10 and 10:1, more preferably less than between 1:5 and 5:1. The weight ratio of the various components of multi-component adhesive composition is adjusted to provide the desired ratio vzaimozachetnykh functional groups.
The amount of catalyst(s)used(s) in a multicomponent system, the binder material can vary significantly in C is depending on the type(s) used(s) of catalyst(s), the desired conditions of solidification and the desired time of presence in the media (freezing time). Optimization levels of catalyst to achieve the minimum time setting when the desired combination of curing conditions will be clear to experts in this field. Guidance on the selection and application of ORGANOMETALLIC catalysts based on transition metal compounds can be found in six patent cited earlier and in the examples below.
Also presented method for the production of lignocellulosic composites. When this method is used the system described above. This method includes the following stages:
a) obtaining a lignocellulosic substrate.
Lignocellulosic substrate preferably contains a lot of lignocellulosic particles bonded material. More preferably, when the lignocellulosic substrate consists essentially of a mass of lignocellulosic particles.
For an arbitrary embodiments of the method of lignocellulosic particles, such as wood chips, can be combined with other powdered materials for inclusion in the final generated by pressing the composite. Non-limiting examples of other powdered materials that can be used with arbitrary embodiment, include chipboard waste from lechenie non-metallic automotive waste, such as waste foam and fabric waste (sometimes referred to collectively as "light pruning"), powder waste plastics, inorganic or organic fibrous substance, a combination of these materials and similar materials. In preferred embodiments of this method the substrate is only lignocellulosic powder material, most preferably of wood shavings (sawdust) used in the production of plates with oriented fibers (DOV). Usually the preferred types of lignocellulosic materials include wood particles and fibers, but you can use other types of lignocellulosic materials or separately, or in combination with material based on wood. Non-limiting examples of alternative lignocellulosic materials suitable for use with this method include agricultural residues such as straw, husks sugarcane, cotton waste, jute and similar materials; waste paper products and paper pulp; combinations of these materials, and the like;
b) obtaining multi-component adhesive compositions containing at least a polyfunctional isocyanate, a hydrophilic polyol and a catalyst.
(C) applying the split and vzaimorezerviruemym components mnogokomponentnoi the adhesive composition for lignocellulosic substrate, preferably in a separate thread without any prior mixing of the components in quantities suitable for the production of product from the associated lignocellulosic composite.
In preferred embodiments of this method vzaimodeistvie components of multi-component adhesive composition applied to the substrate (powder mass) separately from each other. This is preferably done by using separate channels, nozzles or disks for distribution. While the preferred embodiment of the interacting flows of multi-component adhesive composition is not in contact with each other in any degree as long as they will not appear on the surface of the substrate. Although this is usually less preferably, in the broader sense of the scope of the present invention, the interacting components of the adhesive composition is pre-mixed, fully or partially, before application to the substrate. However, when implementing this method with preliminary mixing, it is desirable that the interacting flows of multicomponent adhesive compositions remain separated until immediately when the adhesive mixture is applied on the substrate. Preferably, any mixing of interacting flows must occur within two (2) minutes of applying svyazivayuschego the substance on the substrate, more preferably, within one (1) minute, and more preferably within 30 seconds or less from the application of the binder on the substrate. It is desirable to minimize or prevent reaction between the cooperating threads until, when there is physical contact of the binder with the substrate. When implementing a variant of the method pre-mix vzaimodeistvie streams can be combined with an apparatus for mixing at the point of use, such as a static mixer or mixing by collision. Regardless of whether the mix flows or pre-applied to the substrate separately, in the apparatus for distribution should preferably be provided with tools such as dosing pumps for regulation of the relative amounts of the threads, and the absolute amount of adhesive composition applied to the substrate. Distributing the device should provide a wide and uniform coverage of the substrate by a binder or vzaimorezerviruemym chemical components. Suitable devices such as razbryzgivayuschie head or rotating disks commonly used in the industry of wood composites. If you prefer, you can use other types of devices for distribution. Whichever type of apparatus is La distribution, use, it is preferable that it should provide some degree of atomization flow of chemicals during their application to the substrate.
In preferred embodiments of this method comminuted lignocellulosic substrate, such as a mass of wood shavings (sawdust), loaded into an apparatus for mixing during or immediately after application of multi-component adhesive compositions. In accordance with the latest technology you can use a rotating mixer. Turning helps to ensure uniform distribution of the binder over the entire surface of lignocellulosic particles. Deposition of multicomponent binder while turning milled lignocellulosic substrate is particularly preferable.
Whatever the method of application use, should not be a significant interaction between vzaimorezerviruemym chemical components of multicomponent flows binders before they will be located on the surface of the lignocellulosic substrate. Under the "no significant interaction" is meant that less than 10 mol. %, preferably less than 5 mol. %, more preferably less than 1 mol. %, more preferably less than 0.5 mol. % and most preferably less than 0.1 mol. % of free isocyanate (-NCO) groups, p is outstay in the original composition of multi-component adhesive composition is consumed by the reaction between interacting components of threads before as these flows come into contact with the lignocellulosic substrate;
d) shaping and molding processed a binder lignocellulosic substrate suitable for curing binder conditions and production of products associated lignocellulosic composite.
Processed a binder lignocellulosic substrate, usually crushed the substrate, it is desirable to pour on the template or similar device, which approximates the shape of the final product from lignocellulose. This stage of the process is called forming. During the stage of forming lignocellulosic particles are loosely Packed and prepared to hot pressing. Usually use limiting device, such as a form to prevent ejection of powder fill in the sides. Specialists in this field will understand how to mould processed adhesive composition of the powdered substrate to achieve the desired thickness of the final product extrusion of the composite form. During production of plates pressed in the form (pressed), such as DOV, the operation of molding usually occurs immediately after the application of the binder on the substrate. The final hot pressing of the formed substrate usually occurs within hours of the operation of molding. Gellately is about, to hot pressing would occur as soon as possible after the application of binder to the substrate, although in practice in the production usually is delayed. Preferably, hot pressing occurred within 2 hours of application of the binder, more preferably within 1 hour, more preferably within 30 minutes, and more preferably within 20 minutes. The longer the binder remains in contact with the lignocellulosic substrate and exposed to weathering before pressing, the greater the degree of pre-interaction isocyanate which may occur. The preliminary dimensions of interaction (predetermine) are a function of time, the ambient temperature and humidity environment. Each of these factors, as they may increase in rates tends to increase predetermine. Increased predetermine isocyanate may prevent the development of optimal bonding with an adhesive in the final composite and may result in a composite with poor mechanical properties. Another embodiment is the preparation of wood composites with a separate surface and Central layers. Board with oriented fiber, for example, is constructed using on the ear surface layers and one inner layer, where orientation along the length of the surface and interior flakes changed by 90°. This gives the necessary mechanical properties and dimensional spatial stability of the final composite. Surface and inner layers can be processed or binders based on isocyanates or binders of type FF (phenol formaldehyde resin). While the preferred embodiment uses binder type MDI in both surface and in the inner layer. When treated with a bonding substance, the substrate is formed on a suitable surface, usually mesh or metal plate, known as the leaf cushion formed by the substrate moving in a press and pressing given shape at a temperature of the press and within the time period (time presence in the press), sufficient to ensure that the final curing of the binder. The pressure applied in the press sufficient to achieve the desired thickness and shape of the final composite. Pressing can be conducted at a series of different pressure levels (stages). The maximum pressure is usually between 200 lb/in2and 800 lb/in2but more preferably, from 300 lb/in2up to 700 lb/in2. The total period of stay in the press for a typical manufacturing process DOV, preferably,is between 6 seconds on the panel millimeter thickness and 18 seconds on the panel millimeter thickness, but more preferably, between 8 seconds on the panel mm thickness and 12 seconds on the panel millimeter thickness. Pressing is usually performed using metal plates to apply pressure over the surface of metal plates, called plates pillows. Plate pillows are surfaces which can be in direct contact with the chips treated with a binder (preform for plates) during pressing. Plate pillows usually are plates made of carbon steel, but sometimes use a plate made of stainless steel. The metal surface of the wafer pillows that are in contact with treated a binder lignocellulosic substrate, preferably coated with at least one outer tool for liberation from form to ensure the extraction of the product without damage. External processing to extract from a form suitable for the surfaces of the press used in the production of moldable pressing lignocellulosic product produced from crushed substrates and binders based on isocyanates are well known and their use will be clear to experts in this field. The use of external tools demolding less important when using three who lainy approach (FF top, the binder based on the isocyanate inside), but still desirable. Non-limiting examples of suitable external means for demolding include salts of fatty acids, such as ciliolate soap or other coatings with low surface energy, aerosol medications or layers.
An important advantage of the data of the reaction system and method, as noted earlier, is that the temperature of the pressing can be reduced without increasing term presence in the press. The preferred temperature in the press with this method are in the range from 300°F to 400°F, more preferably from 325°F to 375°F. Especially unexpected feature is that the same advantage of reduced temperature compaction can be achieved, even when using a slower curing binders from FF resins used on the surface. This is surprising because FF binder used for. surface layers, usually require higher temperatures pressing, when using the previous methodology (i.e. with the direct use of MDI in the inner core instead of the multi-component adhesive composition based on isocyanate in accordance with the description);
e) removing the lignocellulosic product.
Utverjdenie pressing the formed product from lignocellulose the aqueous composite is then removed from the press, and any other devices, such as forming the grid and plate separate pillows. Rough edges are usually treated. Sugarexchange products are sometimes subjected to conditioning within the prescribed time under certain ambient temperature and relative humidity to bring the moisture content in the wood to the desired level. This stage of conditioning is optional. In preferred embodiments of this process are formed by molding the product are usually flat plates, such as plates with oriented fibers (PHS). However, the production being formed by pressing lignocellulosic products with a more complex three-dimensional forms is included in the scope of this invention.
In a highly preferred example of embodiment of this method, the catalyst is first mixed with the polyfunctional isocyanate and applied to the substrate in the form of a single jet stream. The hydrophilic polyol is applied to the substrate in the form of the second jet stream. In preferred examples of the process of multi-component adhesive composition is applied to the lignocellulosic substrate in the form of exactly two threads interacting chemical compounds. Streams, most preferably applied to the substrate at the same time, although in a broader sense can apply the ü interactive streams separately in any desired order.
Unexpected and unexpectedly found that these reaction systems and methods facilitate the production of moldable lignocellulosic composites, especially composites formed from the mass of comminuted lignocellulosic material, at lower temperatures the press without increasing the time of presence in the media. In addition, totally unexpected, found that these reaction system and method facilitate the production of lignocellulosic composites of the mass with a relatively high moisture content. You can use the mass having a moisture content greater than 6% by weight, and the pressing can be performed at temperatures press 350°F or slightly below. The moisture content of the mass can be as high as 15% by weight, but preferably ranged between 8% and 14% by weight, more preferably between 9% and 13% by weight of the mass as a whole. This large flexibility in relation to moisture content reduces the need for pre-drying the mass. Preliminary drying can sometimes be completely excluded.
When in the surface layer use FF binder mass, which is used for the surface (FF related) layers may still require drying to reduce moisture levels that are compatible with the use FF binder. However, the main part of the mass, which the traveler goes into the inner layer and is associated with multi-component adhesive system may contain higher levels of moisture (noted above). Well-informed in this field of technology experts will determine the spacing of the levels of humidity mass that is most appropriate for use FF resins as bonding agents.
The reaction systems and methods described herein are particularly suitable for the production of plates with oriented fiber (DOV). However, the reaction systems and methods can be used in manufacturing and other types of moldable pressing lignocellulosic composites. These other types of composites include, but are not limited to, fibre boards (MDF) medium density (MDF; MDF), chipboard (particleboard), plates using a straw, plates using rice bran, plywood, laminated veneer lumber (LVL) and the like.
Molecular weight, equivalent weight and functionality of the groups named here presents the average number for polymeric or oligomeric compounds, unless otherwise specified. Molecular weight, equivalent weight and functionality groups for pure compounds are absolute, unless otherwise indicated. Molecular weight, equivalent weight and functionality groups for mixtures of pure compounds of the same type are average numbers, unless otherwise indicated.
The terms "with coat essentially of", "consists essentially of" and "consisting essentially of" in the context of this description should be understood as meaning that the composition denoted by this term does not contain sufficient quantities of any incremental types of connections (not listed as present) to obtain an appreciable change in the properties or functionality of the composition to which they are relevant to the practical embodiment of this invention.
Specialists in this field will present itself changes are possible within the scope of this invention. The invention is additionally illustrated by the following specific examples, which should not be construed as limiting.
Polyol And initiated glycerin liquid polyester polyol from Huntsman Corporation. This hydrophilic polyester-polyol has an equivalent weight of about 330 and contains more than 50% by weight oxyethylene elements.
From A, polymer polyvinylpolypyrrolidone (PMDI)catalyzed 90 h/m (Fe by weight by weight) of iron acetylacetonate. The polyisocyanate is a mixture of diphenylmethanediisocyanate isomers and higher (3-ring and above) oligomers in a series of MDI. This isocyanate has a content of free isocyanate (-NCO) groups, equal to about 31% by weight and a viscosity at 25°C, equal to about 170 SDR. He and EET average number of functionality isocyanate (-NCO) group, equal to about 2.7.
Breath In, polymer polyvinylpolypyrrolidone (PMDI) from Huntsman Corp. This isocyanate, which has no added catalyst is a mixture of diphenylmethanediisocyanate isomers and higher (3-ring and above) oligomers in a series of MDI. It has a content of free isocyanate (-NCO) groups, equal to about 31% by weight and a viscosity at 25°C, equal to about 170 SDR. He has an average functionality isocyanate (-NCO) group, equal to about 2.7.
EW-58H emulsified wax manufactured by Borden Corp. This substance is a hydrocarbon weak wax, emulsified in water.
GP 3121 and GP 3110 RESI-STRAND® binder liquid fenolfarmaldegidna resin, is used for processing of cereals used in the inner and surface layers, respectively, produced by Georgia Pacific Corp.
Wood chips poplar ocinebrina (poplar) from the University of Maine.
STONER E497 thermosetting agent for demolding produced Stoner Inc.
The procedure of manufacturing wood-shaving plify.
Wood fibers were produced in the Advanced Engineered Wood Composite Center (AEWC), located at the University of Maine at Bangor. Raw timber was felled, shipped and delivered in November 2006, the Raw wood was pulled through the ring of scrutiny the machine Carmanah 12/48, mode at 638 rpm Used two disposable knife that has one angle of 33° and (away) controI with an angle of 70°. The issue of knife established by 0.025" and was measured using a sensor with a circular scale to ensure tolerance not more than +/- 0.002 inch. The chips are then dried to the desired moisture content in a conveyor dryer chip Koch Bros, with forced air at a temperature of about 200°F.
Weighted number of chips corresponding or both surfaces or one core was placed in a spiral rotating blender for connecting substance to the spray disk (Coil spinning disk atomising binder blender). The blender has a 6' diameter, 3' deep and has a rotation of 15 rpm Rotating disk EL-4 was rotated with a speed of about 12,000 rpm
Binder, and where necessary, the polyol was added to the mixer on the basis of weight loss using a Masterflex peristaltic pump using pipe #24 Tygon. Emulsion wax was applied using spray air spray gun, model ¼ JBC SS with the tip of the SU-22 when installing the air pressure to about 20 lbs/inch2. Binder and the wax was injected at a speed of 110 ml/min, whereas the polyol added at the rate of 30 ml/min. Speed for polyol was lower, in order to ensure uniform coating otnositel the small amount of polyol.
Molding was performed using the methods of hand molding. The template 18, steel sheet cushion 4'×8' with thermosetting coating means for demolding STONER E497 was placed on top of the floating bearings table for molding. Then on top of pillows stacked wooden molding box 6"×32"×48". Then formed a three-layer randomly oriented Mat. The mould was then carefully removed and the excess chips on the edges was placed back on the Mat. Around the Mat was placed a sheet of VOC (see next section) and was placed on top of the alignment sheet. This unit is then moved into the press.
System for collecting VOCS (VOC)used to collect discharge from the press consisted of a rigid plate in the frame and install vapour recovery LOS.
Aluminum plate was thick 3/4" sizes VD 41"×89" and sizes ND 46"x 94". The plate had a groove 1/4"×1/4", rounded corners, designed at the top and bottom surfaces, giving the opportunity to place a 6 mm round, sealed cells of the spongy silicone harness. Harness appeared above the surface of the plate, providing a sealing flush during stages of decompression at the end of the pressing cycle.
For a system inlet for air in a closed cushion used intake manifold for the outer is on air coming from the side of the head from front center rear of the frame. Rear connection was made through the pipe, sending the air from the intake manifold through the inlet 5 air holes drilled through the pillow. This gave the opportunity oscillating movements of air through the plate, because the vacuum thrust was created at the front. Stream LOS vapor was pumped through the system output for air, consisting of four holes 1/4"drilled front airbags. These openings are connected with the use of Teflon and copper piping, all leading to one main copper outlet pipe line. This only goes pipeline gave a quick and easy connection of Teflon tubing to the vapor collection system (described below), when a block with a Mat was placed in the press.
The methodology for the collection of gases released during compaction, fully included here by following link: Jiang et al., 2002, Forest Product Journal, 52 (11/12): 66-77.
The Mat 32"x 48" extruded in 4'×8' 1800-ton hydraulic press for hot pressing Erie Mill and Press. The plate was heated to a specified temperature to 350°F (177°C) using two hot oil heaters Mokon, each with two zones. Each plate has 4 built-in fiber optic thermocouple, which recorded the temperature of the tours plates. Programmable logic controller (PLC) controlled the assembled position press the temperature of the plates through second intervals and gave them to the Excel file. Press resulted in positional adjustment to the planned thickness in 0,719". The press was installed at the beginning of its cycle at the beginning of contact of the Mat with both plates (~5,5"). The first stage took 45 seconds to obtain the specified thickness. This position was sustained in the course of from 135 to 240 seconds, depending on processing. Then applied the three-stage decompression, and each lasted 15 seconds.
When the panels were removed from the press, they were marked and then cut into pieces 32"x 80" split table. Then the panels were evaluated for weight, thickness, volume and density. The panel was then subjected to hot-packing.
After pressing, the panels of the panel was kondicionirovanie at 21°C and 41% relative humidity until the final equilibrium moisture content of about 7%. Samples for the determination of physical and mechanical properties were cut from the test panels using pre-defined cut out the pattern.
Volatile organic compounds (VOCS) were analyzed by several analytical methods. LOS or collected in the trap with water or methylene chloride in the unit for collection of VOCS. Used three analytical method for identification and kolichestvennoi evaluation of chemical compounds, present in secretions LOS. Gas chromatography/mass spectrometry (GC/MS) was used for the determination of phenol and benzene present in the methylene chloride. Gas chromatography/flame ionization detector was used for identification and quantification of the amount of methanol present in LOS. Spectrophotometer for ultraviolet radiation (UV) is used to determine the amount of formaldehyde present in aqueous solutions.
Chipboard panels extruded by the above method. Table 1 describes examples of the composition of the panels, which are important for the description. All supplements are presented in parts by weight. Table 2 shows the physical and mechanical properties of the emission in the pressing of panels for each example described in Table 1.
|The details of the construction of the panels and properties panels|
|Details of the structure of the panels||Example 1*||Example 2*||Example 3**|
|Binder for surface/number||Out In/4%||GP 3110 RESI-STRAND/8||From And/4%|
|Binder for the inner layer/number||Out In/4%||GP 3121/8%||From A/4%|
|The wax content||1%||1%||1%|
|The moisture content of the chips on the surface/in the Central part||11/7% SV||5/5% SV||13/11% SV|
|The temperature of extrusion||400°F||400°F||350°F|
|* presents examples to compare|
|** represents an example of description|
|Physical, mechanical properties of secretions during pressing of wood-particle panels|
|Test property||Use the 1*||Example 2*||Example 3**|
|Internal communications (including/thousand)||134||23||128|
|The thickness swelling (%)||4,5||7,2||the 5.7|
|PP (MOR) lb/in2||7019||4764||6588|
|PE (MY) lb/in2||959226||813845||924068|
|Phenolic allocation (hours/thousand)||0||11,5||0|
As can be seen in Table 2, Example 3 shows the improvement of physical and mechanical properties and reduced discharge during pressing in comparison with the liquid phenol-formaldehyde (FF) a binder in Example 2. Cu is IU, Example 3 demonstrates comparable physical and mechanical properties relative to 100% associated MDI panel described in Example 1. In addition, these comparable physical and mechanical properties obtained with a significant decrease in the temperature of extrusion and at high moisture content of the chips. Because of this lower temperature pressing, formaldehyde emissions, and energy for heating the press significantly reduced in Example 3 (comparison Example 1), and Example 3 shows that it is possible to associate lignocellulosic composites at unusually high moisture content of the chips, which allows to save energy and reduce the allocation of drying in the dryer.
The following examples (Examples 4 and 5) show the advantage of adding a polyol separately from connecting MDI substances. DHS prepolymer made by adding 15 parts by weight of polyol And 85 parts by weight binder, From A. These components are then placed in an oven heated to 60°C. for 12 hours. The resulting prepolymer had a percent NCO and a viscosity of about 27% and 650 centipoise at 25°C, respectively. As shown, prepolymer example 5 demonstrates the advantage of adding the two components separately.
|Details of the manufacture of panels and panel properties|
|Details of the composition of the panel||Example 4|
|View binder/number||4% From A||4.6% of MDI of prepolymer|
|The wax content||1,0||1,0|
|The moisture content in the chips||10,0||10,0|
|Temperature pressing (°F)||350||350|
|Physical, mechanical properties of secretions during pressing of wood-particle panels|
|Test property||Example 4|
|Internal communication (lb/in2)||55|
|PP (MOR) lb/in2||4465||2499|
|PE (MY) lb/in2||6460119||470501|
|Test abrasion resistance D-5||477||324|
Comparison of Examples 4 and 5 shows the improvement of the properties of composite panels using adhesive compositions according to this description. The panel, made with binder system according to this description (Example 4), exhibit higher mechanical properties and properties of wear resistance than the equivalent prepolymer, a system with one component (Example 5).
1. Adhesive composition for use in manufacturing molded by extrusion products from lignocellulosic composite containing polyfunctional isocyanate, a simple polyetherpolyols and a catalyst consisting of at least one organic compound of iron and at least one chelating ligand.
2. The adhesive composition according to claim 1, where polyetherpolyols contains more than 50% oxyethylene segments based on the weight of polyol.
3. The adhesive composition according to claim 1, where the polyfunctional isocyanate comprises a mixture of one or more isomer is in dimetilmetabolita and one or more polymethylenepolyphenylisocyanate.
4. The adhesive composition according to claim 1, where polyetherpolyols has srednecenovogo molecular weight between 300 and 10,000, and it is received by the initiator with average functionality of from 2 to 10.
5. The adhesive composition according to claim 4, where polyetherpolyols has content oxyethylene at least 70 wt.%, srednecenovogo molecular weight of between 700 and 2000, and it is received by the initiator with the average number of functionality from more than 2 to 4.
6. The adhesive for use in the manufacture of products from being formed by pressing lignocellulosic composite comprising: (a) a polyfunctional isocyanate, (b) simple polyetherpolyols in which oxyethylene segments constitute more than 50% polyol by weight, and (C) a catalyst comprising at least one organic compound of iron and at least one chelating ligand.
7. Multi-component adhesive composition comprising a polyfunctional isocyanate, a simple polyetherpolyols and a catalyst consisting of at least one organic compound of iron and at least one chelating ligand, and this multi-component adhesive composition is prepared in the form of at least two vzaimorezerviruemym chemical components, where (a) one of the at least two vzaimorezerviruemym chemical components contains the polyfunctional Isola is at and the catalyst, and (b) one of at least two vzaimorezerviruemym chemical components contains polyetherpolyols.
8. Multi-component adhesive composition according to claim 7, where polyetherpolyols contains more than 50% oxyethylene segments based on the weight of polyol.
9. Multi-component adhesive composition according to claim 7, where the polyfunctional isocyanate comprises a mixture of one or more isomers dimetilmetabolita and one or more polymethylenepolyphenylisocyanate.
10. Multi-component adhesive composition according to claim 7, where polyetherpolyols has srednecenovogo molecular weight between 300 and 10,000, and it is derived from the initiator, having an average functionality of from 2 to 10.
11. Multi-component adhesive composition of claim 10, where polyetherpolyols has content oxyethylene at least 70 wt.%, srednecenovogo molecular weight of between 700 and 2000, and it is received by the initiator with the average number of functionality from more than 2 to 4.
12. Method for the production of lignocellulosic composites, comprising the following stages:
(a) obtaining a lignocellulosic substrate, consisting of a set of bonded lignocellulosic pieces;
(b) obtaining a binding composition comprising a polyfunctional isocyanate, polyetherpolyols and a catalyst consisting of at least one organic compound of iron and by at least one chelating ligand, moreover, the adhesive composition is formed as two separate components;
(c) applying two separate components of the adhesive composition on lignocellulosic substrate in quantities suitable for the production of product from the associated lignocellulosic composite;
(d) molding and extrusion lignocellulosic substrate under conditions suitable for curing the binding of the composition and production of products associated lignocellulosic composite; and
(e) removing a product from a lignocellulosic composite.
13. The method according to item 12, where polyetherpolyols contains more than 50% oxyethylene segments based on the weight of polyol.
14. The method according to item 13, where polyetherpolyols has content oxyethylene at least 70 wt.%, srednecenovogo molecular weight of between 700 and 2000, and it is received by the initiator with the average number of functionality from more than 2 to 4.
15. The method according to item 12, where: (a) one of the two separate components contains a polyfunctional isocyanate and a catalyst, and (b) the other component contains a hydrophilic organic polyetherpolyols.
16. Product from a lignocellulosic composite, obtained using multi-component adhesive composition according to claim 7.
17. Lignocellulosic composite obtained by the method according to item 12.
SUBSTANCE: moisture-curable and biodegradable adhesive which contains a reaction product of: (a) an isocyanate component having an average functionality of at least 2, the isocyanate component being selected from a group consisting of lysine diisocyanate and derivatives thereof, lysine triisocyanate and derivatives thereof, and combinations thereof; (b) an active hydrogen component having an average functionality greater than 2.1, the active hydrogen component containing a component with a hydroxyl functional group; and (c) an ionic salt component having an average hydroxyl or amino functionality, or combination thereof, of at least 1, selected from a group consisting of ammonium salts, halides, sulphonates, phosphonates, carboxylates and combinations thereof.
EFFECT: obtaining a moisture-curable and biodegradable adhesive.
18 cl, 1 dwg, 17 ex
SUBSTANCE: adhesive polyurethane composition consists of a prime coat and polyurethane adhesive, comprising urethane rubber and ethyl acetate, applied on its surface. The prime coat consists of a solution of polyurethane thermoplastic elastomer with ethyl acetate in ratio: polyurethane thermoplastic elastomer 10-18 wt % and ethyl acetate - the balance. The polyurethane adhesive contains a solution of polyurethane thermoplastic elastomer and a mixture of polar organic solvents consisting of ethyl acetate and methylene chloride, with the following ratio of components: polyurethane thermoplastic elastomer 17-27 wt %; methylene chloride 7-10 wt % and ethyl acetate - the balance. The polyurethane adhesive can contain perchlorovinyl resin as a target additive in amount of 0-10% to the total weight of the adhesive.
EFFECT: low cost and improved adhesion properties of the adhesive composition and cohesion strength characteristics of the adhesive joints.
2 cl, 2 tbl
SUBSTANCE: composition contains the following in pts.wt: 100 bifunctional prepolymer with terminal isocyanate groups, 10.6-12.8 - 3,3'-dichloro-4,4'-diaminodiphenylmethane, 15.9-19.2 dioctylsebacate, 1.2-1.4 - 1,4-butanediol, 0.31-0.35 - para-phenylenediamine and 0.015-0.030 - Agidol 51,52,53 (mixture of 2-dimethylaminomethylphenol, 4-dimethylaminophenol, 2,6-bis (dimethylaminomethyl)phenol, 2,4-bis-(dimethylaminomethyl)phenol,2,4,6-tris-dimethylaminomethyl)phenol.
EFFECT: obtaining a fixing composition which, after prolonged storage, retains strength and adhesion parameters vital for operation of charges of antitank grenades at both high and low temperatures, and also prevents accidental exposure to substances which are harmful to health of personnel, in cases of technical faults and emergencies.
SUBSTANCE: invention relates to method for covering light airplanes with polyester sheathing fabric, as well as to dispersive hot-gluing glue and its application for covering. For covering, polyester sheathing fabric with longitudinal shrinkage of 7% and transversal shrinkage of 5% at 160-180°C is used. In the process of covering light airplanes and/or their parts consisting of frame system, sheathing fabric in the area of its overhangs and frame parts is covered by dispersive hot-gluing glue and wrapped around longeron part of frame so that when connection between sheathing fabric and frame produced by glue is destructed the fabric could be held on frame carcass. Dispersive hot-gluing glue contains 80-88% of adhesive, 12-15% of hardener and 0.15-0.3% thickener, and the glue is polymerised at temperatures >40°C. The hardener contains 54-60% of solvent, 0.35-0.5% of naphthalensulfonic acid sodium salt-based stabiliser, 0.25-0.35% of propoxylated spirit-based emulsifier, 1.7-1.9% of polyetheramines-based hardener, 37-41% of polyisocyanate.
EFFECT: reliability and durability of light airplanes and/or their parts covering.
15 cl, 3 dwg
SUBSTANCE: invention relates to aldimines of formula (I)
where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.
EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.
22 cl, 18 ex, 6 tbl
SUBSTANCE: present invention relates to a polyisocyanurate based adhesive which is obtained by reacting an organic polyisocyanate with a compound containing hydrogen atoms which are reactive towards isocyanate, in the presence of a trimerisation catalyst. The organic polyisocyanate is a polymer or prepolymer polyisocyanate, and content of the soft block in the adhesive ranges from 40 to 60 wt %. A reaction mixture for producing said adhesive is also described.
EFFECT: obtaining an adhesive capable of withstanding high maximum stress, having extremely fast setting and having a good and strong bond with the base, as well as high thermal stability, resistance to salty water and creep.
9 cl, 4 ex, 6 tbl
SUBSTANCE: method involves applying a UV curable adhesive resin composition, containing a photolatent base, onto at least one transparent surface of at least one of a first and a second substrate. The substrates are then brought together so that said adhesive composition lies in between. The adhesive composition is then exposed to actinic radiation for curing. The UV curable adhesive is a OH/NCO system or SH/NCO system. In another version of the gluing method, the first and second substrates are brought together after exposing the adhesive composition in between to actinic radiation.
EFFECT: disclosed gluing method enables faster curing of the adhesive.
5 cl, 10 tbl, 6 ex
SUBSTANCE: composition contains one or more urethane prepolymers, having isocyanate residues, one or more compounds which catalyse the reaction of isocyanate residues with water or a compound which contains active hydrogen and one or more alpha-hydrocarbyl silane compounds. The urethane propolymer additionally contains a silane functional group. The composition additionally contains a compound or a polymer, containing silane residues. The composition additionally contains one or more compounds which catalyse silanol condensation. The composition is deposited onto the surface of glass or plastic with a coating or onto the surface of a substrate to obtain a sealant, then brought into contact and the composition is then hardened. The composition is placed between the glass or plastic with coating and the substrate. The sealing composition is used for binding an unprimed surface with a coating, such as a window lintel with glass with a transparent plastic, coated with an abrasive-resistant coating or with glass or plastic with a coating, additionally coated with glass cement, such as ceramic or organic glass cement.
EFFECT: improved composition properties.
10 cl, 2 ex
SUBSTANCE: invention relates to a method of producing dispersions of blocked polyurethane prepolymers, use of dispersions obtained using said method to produce coating agents, adhesive substances and sealants and elastomers, said application products themselves, as well as substrates provided with coating agents. The method involves the following: I) a blocked polyurethane prepolymer is obtained first by reacting a) 100 equivalent % of at least one polyisocyanate with b) 50-90 equivalent %, in terms of isocyanate reactive groups, of a thermally split blocking agent, c) 5-45 equivalent %, in terms of isocyanate reactive groups, monohydroxycarboxylic acid as a hydrophilic agent and d) 0-25 equivalent %, in terms of isocyanate reactive groups, of polyhydroxycarboxylic acid as a hydrophilic agent and e) 0-15 equivalent %, in terms of isocyanate reactive groups, of at least one, in terms of isocyanate reactive groups, di- or polyfunctional component of a chain extender with molecular weight from 32 to 350 g/mol, where i) this takes place using (partially) water-miscible organic solvents which are inert to NCO-groups and have boiling point lower than 120°C (at 1013 mbar), ii) and they are used in such an amount that the polyurethane prepolymer contained in the reaction solution after complete conversion ranges from 70 to 98 wt %. Further, II) the polyurethane prepolymer solution obtained at step (I) is dispersed in water, where before, during or after dispersion, deprotonation of carboxylic acid groups with a base takes place at least partially, and then III) if needed, the contained organic solvent is completely removed during dispersion via distillation.
EFFECT: obtaining polyurethane dispersions which are stable during storage, endow said products of their application with good optical properties, high resistance to chemical reagents and pendulum hardness.
13 cl, 10 ex, 1 tbl
SUBSTANCE: adhesive composition contains perchlorovinyl resin and an organic solvent. The composition contains dichloroethane as an organic solvent, as well as dibutyl phthalate and a modifier in form of epoxy diane resin ED-20 and N-nitrosodiphenylamine, with the following ratio of components in pts.wt: perchlorovinyl resin 20, organic solvent 80.0, dibutyl phthalate 1.0, epoxy diane resin ED-20 10.0-15.0, N-nitrosodiphenylamine 0.33-1.11.
EFFECT: invention increases strength when gluing together vulcanised rubber.
FIELD: machine building.
SUBSTANCE: invention can be used for manufacture of elastic support hinges (ESH) of nozzle blocks of solid-propellant rocket engines (SPRE). Die mould for manufacture of reinforced rubber technical goods with layer-by-layer located reinforcement elements and layers of elastomer includes upper and lower semi-moulds, and upper and lower forming rings, as well as fasteners of reinforcement elements. Upper and lower hold-down rings rigidly attached to the corresponding moulding rings are installed opposite fasteners of reinforcement elements. One hold-down ring is equipped with screws screwed into threaded through holes open in that ring against the stop into fasteners of reinforcement elements. Through slots for passage of elastomer to reinforcement elements are made in the other hold-down ring.
EFFECT: number of die moulds of the design as per the described invention has been developed by the enterprise, where high-quality ESH of nozzle blocks with various dimensions are manufactured and the required manufacturability is provided.
FIELD: machine building.
SUBSTANCE: invention refers to manufacturing technology of reinforced rubber technical goods by vulcanisation in a die mould, and can be used for manufacture of elastic support hinges (ESH) of nozzle blocks of solid-propellant rocket engine (SPRE). Die mould for manufacture of reinforced rubber technical goods with layer-by-layer located spherical reinforcement elements and elastomer layers includes a loading chamber and a moulding block with upper and lower fasteners of reinforcement elements made in the form of a rigid rack with teeth. Teeth of fasteners of reinforcement elements are inclined in relation to longitudinal rack axis and located at an angle to it, the value of which varies as to the rack length and is determined by the following formulae: α=90°+βu-arcsin rli/Ri for upper fastener of reinforcement elements; δ=90°+βl-arcsin rli/Ri for lower fastener of reinforcement elements, where i - ordinal number of reinforcement element; βu - deflection angle of upper edge of reinforcement elements from vertical plane; βl - deflection angle of lower edge of reinforcement elements from vertical plane; Ri - radius of spherical surface of i reinforcement element; rui - circle radius of upper edge of i reinforcement element; rli - circle radius o flower edge of i reinforcement element. Use in moulding block of die mould of fasteners made considering the curvature of spherical reinforcement elements, which is variable as to thickness of pack of ESH, provides the setting of similar gaps and simplifies the installation of fasteners between spherical reinforcement elements during assembly of the die mould.
EFFECT: row of high-quality ESH of large-size nozzle blocks of SPRE is made in the die mould and the required manufacturability is provided.
SUBSTANCE: described is a liquid graft polymer obtained using a method which involves reaction of a polymer of a C4-C7 monoolefin monomer and a C4-C14 multiolefin monomer which contains butyl rubber, in the presence of a material for conducting graft copolymerisation, which contains maleic anhydride, and a free-radical polymerisation initiator which contains an organic peroxide, wherein the liquid graft polymer has number-average molecular weight (Mn) from 150000 to 30000. Described is a vulcanised compound containing the described liquid graft polymer and a vulcanising agent based on a multi-functional amine. Described is a method of decomposing a non-liquid butyl polymer to a liquid butyl graft polymer, where the method involves reaction of a non-liquid butyl polymer of a C4-C7 monoolefin monomer and a C4-C14 multiolefin monomer which contains butyl rubber, in the presence of a material for conducting graft copolymerisation, which contains maleic anhydride, and a free-radical polymerisation initiator containing dicumyl peroxide, wherein the liquid graft polymer has number-average molecular weight (Mn) from 150000 to 30000.
EFFECT: liquid maleated butyl rubber is obtained.
16 cl, 2 tbl, 2 dwg, 10 ex
FIELD: process engineering.
SUBSTANCE: invention relates to setting of thermosetting material. Proposed method comprises steps whereat material is heated by heating fluid. Then, material electrical or optical properties are measure by setting transducer. Besides, heating fluid temperature is adjusted to comply with measured characteristics.
EFFECT: faster response of control system.
18 cl, 6 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to curing of rubber articles, for example, tires and tire treads. In compliance with this method, one or several rods with high thermal conductivity are used in mould to direct heat to article curing-limiting parts. One or several rods with high thermal conductivity are placed in mould at points that allow heat transfer to article curing-limiting part.
EFFECT: decreased curing interval, higher uniformity of curing.
15 cl, 10 dwg
FIELD: process engineering.
SUBSTANCE: proposed method comprises processing material consisting of, at least, first and second parts. Note here that said material is a semi-finished product to be subjected to thermal treatment by electromagnetic power so that said first and second parts are heated in dissimilar ways. At the stage of unequal heating, viscosity of said first part is decreased to render said part a fluid, while second viscosity is, mainly, unchanged or insignificantly reduced. After heating, first and second parts are shaped or moulded to get finished product. Proposed system comprises semi-finished product holder including heating device and shaping or moulding sections. Invention covers also the composition of material made up of two parts.
EFFECT: simplified and efficient process.
32 cl, 13 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to production of engineering rubber articles and is intended for curing reinforced rubber articles in moulds. Proposed mould is intended for curing stack-arranged articles and comprises top and bottom mould halves, reinforcement retainers and extractor. It incorporates no additional mechanisms between heating elements and moulding surface. Every retainer is made up of stepped rod with fixed distance between steps equal to preset distance between reinforcement elements.
EFFECT: higher efficiency and stability of rigidity properties.
SUBSTANCE: invention relates to automotive industry. proposed pneumatic tire has tread surface (1) where contact areas (6, 8, 12, 13 and 14) are limited by grooves (2, 3, 4, 5, 7, 8, 9 and 10). Contact areas (6, 8, 12, 13 and 14) have tread surface sections (6a, 8a, 12a, 13a and 14a) wherein multiple cuts (15) passing in zigzag way along tire width are arranged in preset intervals in direction (T) along tire periphery. Small groove (16) suns between cuts (15 and 15), adjacent in direction (T) along tire periphery. Small groove (16) is so arranged that contact area parts (x and x) segmented on opposite sides of small groove (16 ) are not separated but partially interconnected.
EFFECT: higher stability in turns on wet road coating.
3 cl, 4 dwg
FIELD: machine building.
SUBSTANCE: mould for vulcanisation of hollow rubber-cord items consists of upper and lower half-moulds creating moulding surface of item and of moulding curing diaphragm composed of two parts - external and internal. Textile threads are arranged between parts of the curing diaphragm. Also there are made holes in the toroid part of the diaphragm; the holes facilitate air and vulcanisation gases supply from a cavity between the item and diaphragm to textile fuses performing function of gas outlets.
EFFECT: upgraded quality of item due to improved air and vulcanisation gases outlet between item and diaphragm.
2 cl, 3 dwg
FIELD: production processes.
SUBSTANCE: invention refers to procedure and equipment for vulcanisation of general rubber items, namely to press moulds and vulcanisation method of rubber-chord sleeve-type items. The effect is achieved with press mould for vulcanisation of rubber-chord sleeve-type items, which includes upper and lower half-moulds. At that, press mould includes curing bag so that heat carrier of required pressure is supplied to it, base rings which comprise forming surface, and cone semi-rings which finally form edge of the item and provide tension of chord threads.
EFFECT: improving quality of items and simplifying vulcanisation process of rubber-chord sleeve-type items.
SUBSTANCE: invention relates to a sealing unit designed for use on a line for manufacturing of building panels. In the specified line the mortar is transferred on a movable conveyor relative to the support frame, and cut fibres are placed onto the mortar. The device comprises the first and second extended shafts arranged as a whole. Both shafts are attached as capable of rotation to the support frame and comprise accordingly the first and second sets of discs spaced along the axis and axially attached to them. At the same time between the neighbouring discs on the first and second shafts there are grooves formed being an external peripheral edge of the appropriate shaft. Besides, the first shaft is arranged at one level along the horizontal line relative to the second shaft and so that the specified discs are located as alternating with each other, and when looking at it, peripheries of the discs of the first and second sets cover each other.
EFFECT: elimination of clogging and damage of a device with lumps or a hardening mortar.
9 cl, 8 dwg