CN111958746B - Polyurethane urea dispersoid, adhesive composite material and application of polyurethane urea dispersoid and adhesive composite material in preparation of aldehyde-free added ultrathin high-density fiberboard - Google Patents
Polyurethane urea dispersoid, adhesive composite material and application of polyurethane urea dispersoid and adhesive composite material in preparation of aldehyde-free added ultrathin high-density fiberboard Download PDFInfo
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- CN111958746B CN111958746B CN202010822485.8A CN202010822485A CN111958746B CN 111958746 B CN111958746 B CN 111958746B CN 202010822485 A CN202010822485 A CN 202010822485A CN 111958746 B CN111958746 B CN 111958746B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/5042—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing ureum groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
Abstract
The invention discloses an adhesive composition material, which comprises polyisocyanate and a polyurethane urea dispersoid, wherein the solid mass of the adhesive composition material is taken as a reference, the polyisocyanate accounts for 95-99.5%, the preparation raw material of the polyurethane urea dispersoid comprises a) at least one polyurea polyol, the polyurea polyol has the number average molecular weight Mn of more than or equal to 500 and less than or equal to 3000g/mol, the hydroxyl functionality of more than or equal to 1.5 and less than or equal to 4, and one or more hydrophilic compounds containing ionic groups, potential ionic groups and nonionic groups; b) at least one polyester polyol; c) at least one isocyanate; d) a hydrophilic compound containing one or more of an ionic group, a potentially ionic group, and containing 2 to 3 NCO-reactive functional groups; e) optionally blocking agents for isocyanate groups.
Description
Technical Field
The invention belongs to the field of artificial board manufacturing, and relates to a polyurethane urea dispersion, an adhesive composite material prepared from the polyurethane urea dispersion, and an application of the adhesive composite material in preparation of a fiberboard, in particular to a fiberboard with zero aldehyde addition and ultrathin high density.
Background
The production of the ultrathin high-density fiberboard taking urea-formaldehyde resin as an adhesive gains good market evaluation, expands and extends the application of the medium/high-density fiberboard and is mainly used for gift packaging, modeling furniture, circuit control surface boards, automobile interior trim splints and the like.
CN110154198A uses special cooking aids such as sodium hexafluorophosphate and the like to improve the mechanical property of the fiber obtained by hot grinding, improve the strength of the chemical bond of the fiber polymer, prevent the fiber from being easily broken, improve the stability of the space structure of the fiber polymer, and bond the fiber by using urea-formaldehyde resin adhesive to manufacture the ultrathin high-density fiberboard with ultralow formaldehyde release. CN110154198A nanometer antimony trioxide/PP composite fiber is added into the cooking material to reduce the gap of the wood fiber and increase the density of the wood fiber, and the montmorillonite/zirconium dioxide nanometer composite particle and maleic anhydride grafting coupling agent are utilized to prepare a high-performance high-density fiberboard.
With the increasing promotion of people to the environmental protection concept, although the zero-formaldehyde addition ultrathin high-density fiberboard is continuously developed, no technical scheme suitable for industrialization is found in the market so far. CN109605535A discloses a method for manufacturing a 1.5mm ultrathin high-density fiberboard by using aldehyde-free tannin, lignin and starch adhesives, but the traditional biomass adhesives have low strength and are easy to decay, so that the method also has technical obstacles on batch production.
Polyurethane glue is used as an aldehyde-free adhesive to prepare common fiber boards, but the production process of the ultrathin high-density fiber boards is difficult to realize industrial continuous production due to the conveying difficulty caused by low strength of the board blanks. Because the stacking density of the polyurethane glue sizing fiber is half of that of the urea glue fiber, and the fibers have no initial viscosity, the polyurethane glue sizing fiber is paved and stacked in a fluffy state, and is difficult to reach a certain prepressing thickness compared with urea-formaldehyde resin.
During the production process, the linear speed of the ultrathin plate can reach 200m/min at most, and during the high-speed transmission process, the opening position of the prepressing machine generates instantaneous upward force on the fiber plate blank due to the rapid lifting of the prepressing net belt. The isocyanate glue sizing fiber has no initial strength, the surface of a plate blank is still loose after prepressing, the rebound of the isocyanate glue sizing fiber is larger than that of urea glue fiber, and the isocyanate glue sizing fiber can be rapidly brought up to be broken under the action of force. The pre-pressed plate blank is broken due to lack of initial strength at the plate blank transmission interface, and once the pre-pressed plate blank is broken, fibers at the steam-injection opening or the inlet of the hot press are accumulated, so that the machine is stopped to influence production. In addition, because the transmission speed is high, the resistance at the interface can be amplified, a large impact force is generated on the plate blank, the requirement on the compactness of the fiber is high, and the conventional isocyanate glue sizing fiber is difficult to pass through the interface.
Therefore, the preparation of the ultra-thin high-density fiberboard without aldehyde addition inevitably increases the initial strength of the board blank on the basis of ensuring the bonding strength, and the industrialized mass production of the fiberboard can be ensured.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a polyurethane urea dispersion and an adhesive composition formed by the polyurethane urea dispersion and polyisocyanate, which are applied in a fiberboard in a composition form to prepare a zero-aldehyde added ultrathin high-density fiberboard.
The adhesive composition material disclosed by the invention takes polyisocyanate as a main adhesive, and reacts with water to form polyurea to form strong bonding force in a hot pressing stage, and meanwhile, rich N ═ C ═ O groups before hot pressing (a prepressing stage) and active hydrogen in a polyurethane urea dispersoid form multiple hydrogen bond actions, so that certain bonding property before hot pressing can be ensured under the condition of ultralow addition amount of the polyurethane urea dispersoid, namely, high initial strength of a plate blank is realized under the condition of low cost increase, and the fiber plate blank can smoothly enter the hot pressing stage.
In order to achieve the above objects and achieve the above results, the present invention adopts the following technical solutions:
in a first aspect of the present invention, there is first provided a polyurethaneurea dispersion obtained by reacting reactants comprising:
a) at least one polyurea polyol having a number average molecular weight Mn of not less than 500 and not more than 3000g/mol, a hydroxyl functionality of not less than 1.5 and not more than 4 and containing one or more hydrophilic compounds of ionic groups, potentially ionic groups and non-ionic groups;
b) at least one polyester polyol;
c) at least one isocyanate;
d) at least one hydrophilic compound containing one or more of an ionic group, a potentially ionic group and containing 2-3 NCO-reactive functional groups;
e) optionally blocking agents for isocyanate groups.
The total amount of the components a) to e) is 100 parts by weight, and the use amount of each component is as follows:
10 to 85 parts by weight, preferably 40 to 70 parts by weight, of component a);
the component b) is 7 to 30 parts by weight, preferably 10 to 30 parts by weight;
component c) is 5 to 40 parts by weight, preferably 15 to 30 parts by weight;
component d) is from 0.3 to 10 parts by weight, preferably from 0.3 to 5 parts by weight;
component e) is from 0 to 15 parts by weight, preferably from 0 to 8 parts by weight.
In the present invention, the component a) polyurea polyol is selected from one or more compounds represented by the following structural formula:
in the formula, R1Alkoxy selected from C1-C14, preferably CAlkoxy of 3 to C14, more preferably CH3(CH2)3O-、CH3(CH2)7O-、CH3CH(CH3)O-、CH3(CH2)11O-、CH3(CH2)12O-or CH3(CH2)13O-；
R2Alkylene with carboxyl, carboxylate or sulfonic acid group and sulfonate selected from C1-C10, cycloalkyl with carboxyl, carboxylate or sulfonic acid group and sulfonate with C7-C16, or ether group with carboxyl or sulfonic acid side group with C3-C16; preferably C3-C10 alkylene with carboxyl, carboxylate or sulfonic acid group, sulfonate, or C7-C10 cycloalkyl with carboxyl, carboxylate or sulfonic acid group, sulfonate; further preferred is
R3An alkylene group selected from the group consisting of C1 to C10, more preferably- (CH)2)6-。
In the present invention, the component b) polyester polyol is selected from one or more polyester polyols with Mn of 1000-10000g/mol and functionality of 2-4, preferably from one or more polyester polyols with Mn of 1000-3000g/mol and functionality of 2-4, more preferably from one or more polyester diols with Mn of 1000-3000 g/mol. Suitable polyester diols include one or more of polycaprolactone diols, polycarbonate diols, polyethylene adipate diols, poly-1, 4-butanediol adipate diols, poly-neopentyl glycol adipate diols, poly-1, 6-hexanediol adipate diols, and poly-neopentyl glycol adipate-1, 6-hexanediol adipate diols.
In the present invention, the isocyanate of component c) is selected from one or more of aliphatic isocyanate, alicyclic isocyanate and aromatic isocyanate, more preferably from aliphatic isocyanate and/or alicyclic isocyanate, for example, from one or more of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate trimer, dodecamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate.
In the present invention, the component d) is a hydrophilic compound having an ionic group and 2 to 3 NCO-reactive functional groups and/or a hydrophilic compound having a latent ionic group and 2 to 3 NCO-reactive functional groups, preferably selected from one or more of diaminosulfonic acid and salts thereof, diaminocarboxylic acid and salts thereof, dihydroxycarboxylic acid and salts thereof, dihydroxysulfonic acid and salts thereof, more preferably selected from diaminocyclohexanecarboxylic acid, N- (2-aminoethyl) -2-aminoethanesulfonic acid and alkali metal salts and/or ammonium salts thereof, N- (3-aminopropyl) -3-aminopropanesulfonic acid and alkali metal salts and/or ammonium salts thereof and N- (2-aminoethyl) -3-aminopropanesulfonic acid and alkali metal salts and/or ammonium salts thereof Or one or more of ammonium salts.
In the present invention, the component e) is, for example, one or more selected from methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-N-propylamine, morpholine, piperidine, 2-amino-2-methyl-1-propanol and diethanolamine, more preferably diethanolamine.
The preparation of the aqueous polyurethane urea dispersion can be carried out by conventional methods, for example, by the following steps:
mixing the component a), the component b), the component c) and the component e) with a catalyst in proportion, and then carrying out polymerization reaction to form an isocyanate-terminated polyurethane prepolymer; carrying out chain extension reaction on the obtained polyurethane prepolymer and the component d), and then dispersing in water or adding water into a mixture obtained after the chain extension reaction for dispersion to obtain a polyurethane urea aqueous dispersion;
wherein, when the polyurea polyol contains carboxyl groups and sulfonic acid groups or the component d) contains carboxyl groups and sulfonic acid groups, a neutralizing agent is added to adjust the pH of the dispersion to 7-8, the neutralizing agent can be one or more, preferably, tertiary amines, such as trialkylamines, and the tertiary amines are more preferably one or more, such as trimethylamine, triethylamine, methyldiethylamine, tripropylamine, dimethylcyclohexylamine, N-methylmorpholine and diisopropylethylamine, and are more preferably triethylamine.
The aqueous polyurethane urea dispersion has a solid content of 10-65 wt%, preferably 40-60 wt%.
In the method of the invention, the catalyst used is a heavy metal organic compound with a catalytic function, which is conventional in the field, and comprises an organotin catalyst, an organozinc catalyst and an organobismuth catalyst, and the organobismuth catalyst is preferred.
In a second aspect of the present invention, an adhesive composition is provided, which includes a polyisocyanate (component B) and the above-mentioned polyurethaneurea dispersion (component a), wherein the amount of the polyisocyanate is 95 to 99.5%, preferably 98 to 99%, based on the solid mass of the adhesive composition (i.e., the sum of the solid content of the component a and the mass of the component B).
In the present invention, the polyisocyanate is polymethylene polyphenyl polyisocyanate and/or a derivative thereof, preferably polymethylene polyphenyl polyisocyanate having NCO% of 29-35% and viscosity of 150-250cp (25 ℃). May be a polyisocyanate of the Wannate series from Wannate chemical group, ltd, for example, PM-100, PM-200, PM-400, PM-600, PM-700, CW20, CW30, PM300E, 9132 FC.
In the adhesive composition material, the polyurea polyol modified by the hydrophilic compound with a special structure is used, so that the solubility of polyurea in the polyurethaneurea is improved, meanwhile, the proportion of polyurea chain segments in a dispersion is increased, the polarity of a polymer is increased by carbamido, and the initial viscosity of the polyurethaneurea dispersion is improved;
furthermore, the content of active hydrogen in the polyurethane urea dispersoid is greatly increased by the promotion of the polyurea chain segment, isocyanate is easy to spread and permeate on the surface of the fiber before hot pressing in a wood fiber system taking polyisocyanate as a main adhesive, N ═ C ═ O group strong electronegativity nitrogen atoms and oxygen atoms in the isocyanate and a large amount of active hydrogen in the polyurethane urea dispersoid form strong hydrogen bonding action, the traditional quadruple hydrogen bonding action between polyurethane urea molecules is promoted to the eight hydrogen bonding action between isocyanate and polyurethane urea dispersoid to form an effective [ fiber-polyurea-polyurethane urea-polyurea-fiber ] structure, a connecting structure formed by strong intermolecular force is built between the fiber and the fiber, and the initial strength of a plate blank is greatly promoted on the basis of the initial viscosity of the polyurethane urea dispersoid from height. After hot pressing, the polyisocyanate forms a large amount of polyurea structures, so that the fiber is ensured to be formed into a board, and various mechanical indexes are met.
The adhesive composition material can be applied to preparation of zero-aldehyde addition ultrathin high-density fiberboard.
In another aspect of the present invention, there is provided a method for preparing an ultra-thin high-density fiberboard with zero aldehyde addition, comprising:
s1: a wood chip treatment process: peeling the raw wood, and chipping the wood raw material into wood chips with the length of 3-5 cm, the width of 20-25 cm and the thickness of 1.5-2.5 cm by a chipping machine; the wood chips are preheated by a preheating bin, the preheating temperature is 90-98 ℃, the cooking temperature is 170-180 ℃, the cooking pressure is 7.5-8.0 bar, and the time is 2.5-3 minutes. Through the wood chip treatment process, the water content of the wood chips is homogenized, and the fiber separation efficiency and the fiber separation uniformity are improved;
s2: a fiber preparation process: the wood chips enter a hot mill through a belt type screw, the gap between grinding discs is controlled to be less than or equal to 0.25mm, the length of the prepared wood fiber is 1.5-4 mm, and the length-width ratio is greater than or equal to 60;
s3: sizing: pumping the component A into an inlet in a spraying pipe through a sizing pump, pumping the component B into an inlet of the spraying pipe through another sizing pump, spraying the component A and the component B on fibers through a high-pressure nozzle, and uniformly mixing the component A and the component B with the fibers;
s4: a drying procedure: after sizing, drying for 7-10s, and controlling the water content of the fiber to 7.8-10 wt%;
s5: a separation process: removing foreign matters such as rubber blocks, fiber clusters, fiber bundles and the like;
s6: paving and prepressing: paving the fibers by a plurality of groups of leveling rollers, then pre-pressing the plate blank at the pressure of 15-18 MPa, and trimming the plate blank;
s7: hot pressing: the hot pressing temperature is 230-160 ℃, a five-section hot pressing temperature area is adopted, the hot pressing pressure is 0-40 MPa, and the hot pressing speed is as follows: 150-200 m/min;
s8: and (3) post-treatment process: cooling and curing for more than 72h, and sawing. The ultrathin plate production line does not need a plate turning cold press, and hot-pressed plates are sawed into plain plates with specification and size.
In the present invention, the pressures are gauge pressures.
The invention has the beneficial effects that:
1. the polyurea polyol with a special structure and high active hydrogen content is introduced and matched with other components to obtain the polyurethane urea dispersoid with excellent initial viscosity, and in the production and manufacture of the zero-formaldehyde ultrathin addition fiber board, higher initial strength of the board blank can be realized in a pre-pressing stage, and meanwhile, the polyurea structure formed by isocyanate ensures the extremely strong bonding strength of the fiber board, so that the zero-formaldehyde ultrathin addition fiber board with excellent performance is obtained;
2. the initial adhesion effect can be realized by controlling the addition amount of the polyurethane urea dispersoid to be 0.5-1%, the initial strength of the pre-pressed slab is ensured, and the cost advantage is obvious.
Detailed Description
The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The main raw material sources are as follows:
the polyurea polyol has the following structure:
polyurea polyol I (product of wawa chemistry):
wherein R is1Is CH3(CH2)13O-，R2Is composed of
R3Is- (CH)2)6-; hydroxyl value is 116mg KOH/g;
polyurea polyol ii (product of wawa chemistry):
wherein R is1Is CH3(CH2)11O，R2Is composed of
R3Is- (CH)2)6-; hydroxyl value is 123mg KOH/g;
polyurea polyol iii (wanhua chemistry):
wherein R is1Is CH3(CH3)7O，R2Is composed of
Polyester polyol I:
hydroxyl number 56mg KOH/g (polycaprolactone diol, Mn 2000g/mol, warfarin chemical);
polyester polyol II:
hydroxyl number 37mg KOH/g (poly 1, 6-hexanediol adipate diol, Mn 3000g/mol, wakaki chemistry);
isocyanate I: hexamethylene diisocyanate trimer (N3300, NCO content 21.8%, Bayer);
isocyanate II: isophorone diisocyanate (
IPDI, NCO content 37.5%, wanhua chemistry);
CW 20: a mixture of polyfunctional isocyanate and diphenylmethane diisocyanate having an NCO content of 30.5%, a wanhua chemistry;
9132 FC: polyfunctional isocyanate derivatives having an NCO content of 30.0%, Vanhua chemistry.
Example 1
50 parts by mass of a polyurea polyol I subjected to dehydration treatment, 19.3 parts by mass of an isocyanate II, 20 parts by mass of a polyester polyol I subjected to dehydration treatment, 2.37 parts by mass of diethanolamine, and 0.1 part by mass of bismuth neodecanoate were put into a 50L reactor equipped with a stirrer, a thermometer, and a condenser, and the mixture was stirred at 80 to 90 ℃ until NCO reached 0.72%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 8.33 parts by mass of sodium N- (2-aminoethyl) -2-aminoethanesulfonate and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved, and the mixture was stirred for 20 minutes to sufficiently disperse the mixture, and the pH of the aqueous dispersion was adjusted to 8 using triethylamine. After high-speed emulsification and separation of the acetone by distillation under reduced pressure, an aqueous polyurethane urea dispersion is obtained which has a solids content of 50% by weight.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 1 percent of the solid content of the composite material;
CW20 accounting for 99 percent of the solid content of the composite material; namely, 2 parts by mass of the A component and 99 parts by mass of the B component, the same applies below.
Example 2
In a 50L reactor equipped with a stirrer, a thermometer and a condenser, 43 parts by mass of a dehydrated polyurea polyol II, 27.3 parts by mass of an isocyanate I, 22 parts by mass of a dehydrated polyester polyol II, 1.84 parts by mass of N-methyl-N-propylamine and 0.15 part by mass of bismuth neodecanoate were charged and the mixture was stirred at 80 to 90 ℃ until NCO reached 0.53%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 5.86 parts by mass of sodium N- (3-aminopropyl) -3-aminopropanesulfonate and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved while vigorously stirring for 20min to sufficiently disperse, and the pH of the aqueous dispersion was adjusted to 7.8 using triethylamine. After high-speed emulsification and separation of the acetone by distillation under reduced pressure, an aqueous polyurethane urea dispersion is obtained which has a solids content of 50% by weight.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 1.5 percent of the solid content of the composite material;
9132FC, accounting for 98.5 percent of the solid content of the composite material.
Example 3
39 parts by mass of a polyurea polyol III subjected to dehydration treatment, 19.45 parts by mass of an isocyanate I, 30 parts by mass of a polyester polyol I subjected to dehydration treatment, and 8.6 parts by mass of diethanolamine are put into a 50L reaction kettle equipped with a stirrer, a thermometer, and a condenser, and 0.08 part by mass of bismuth neodecanoate is stirred at 80 to 90 ℃ until NCO reaches 0.68%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 2.95 parts by mass of N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved while vigorously stirring. After stirring for 20min for thorough dispersion, high-speed emulsification and separation of the acetone by distillation under reduced pressure, an aqueous polyurethane urea dispersion is obtained which has a solids content of 50% by weight.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 1.2 percent of the solid content of the composite material;
9132FC, accounting for 98.8 percent of the solid content of the combined material.
Example 4
In a 50L reactor equipped with a stirrer, a thermometer and a condenser, 65 parts by mass of a dehydrated polyurea polyol III, 21.06 parts by mass of an isocyanate I, 10 parts by mass of a dehydrated polyester polyol I, 3.56 parts by mass of N-methyl-N-propylamine and 0.26 part by mass of bismuth neodecanoate were charged and the mixture was stirred at 80 to 90 ℃ until NCO reached 0.49%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 0.38 part by mass of N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved while vigorously stirring. After stirring for 20min for thorough dispersion, emulsification at high speed and separation of acetone by distillation under reduced pressure, an aqueous polyurethane urea dispersion is obtained which has a solids content of 50% by weight.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 0.8 percent of the solid content of the composite material;
CW20 accounting for 99.2 percent of the solid content of the composite material.
Example 5
In a 50L reactor equipped with a stirrer, a thermometer and a condenser, 58 parts by mass of a dehydrated polyurea polyol I, 19.89 parts by mass of an isocyanate I, 17.91 parts by mass of a dehydrated polyester polyol II and 0.17 part by mass of bismuth neodecanoate were charged and the mixture was stirred at 80 to 90 ℃ until NCO reached 0.53%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 4.2 parts by mass of sodium N- (3-aminopropyl) -3-aminopropanesulfonate and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved while vigorously stirred for 20min to sufficiently disperse, and the pH of the aqueous dispersion was adjusted to 7.8 using triethylamine. After high-speed emulsification and separation of the acetone by distillation under reduced pressure, an aqueous polyurethane urea dispersion is obtained which has a solids content of 50% by weight.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 1.5 percent of the solid content of the composite material;
9132FC, accounting for 98.5 percent of the solid content of the composite material.
Comparative example 1 (No polyurea polyol used)
In a 50L reactor equipped with a stirrer, a thermometer and a condenser, 75 parts by mass of dehydrated polyester polyol I, 18.78 parts by mass of isocyanate I, 3.38 parts by mass of diethanolamine and 0.15 part by mass of bismuth neodecanoate catalyst were charged and the mixture was stirred at 80 to 90 ℃ until NCO reached 0.67%. The obtained prepolymer was dissolved in 100 parts by mass of acetone and cooled to 48 ℃. 2.84 parts by mass of N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt and 100 parts by mass of water were added to an acetone solution in which the prepolymer was dissolved while vigorously stirring. After stirring for 20min for thorough dispersion, an aqueous polyurethane urea dispersion having a solids content of 50% by weight was obtained after separating off the acetone by distillation under reduced pressure.
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the solid content of the polyurethane urea aqueous dispersion accounts for 1 percent of the solid content of the composite material;
CW20 accounting for 99 percent of the solid content of the composite material.
Comparative example 2 (without the use of a polyurethaneurea dispersion)
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a is polyurethane urea aqueous dispersion, the consumption is 0;
CW20 accounting for 100 percent of the solid content of the composite material;
comparative example 3 (use of Polyurethaneurea Dispersion only)
The composite material for the zero-aldehyde added ultrathin high-density fiberboard is as follows:
a, the polyurethane urea aqueous dispersion prepared in the example 1 is used, and the solid content of the polyurethane urea aqueous dispersion accounts for 100 percent of the solid content of the composition;
b: CW20, accounting for 0 percent of the solid content of the composite material.
The polyurethaneurea dispersion compositions obtained in each of examples and comparative examples were carried out on a high density fiberboard (1mm) continuous production line to prepare an aldehyde-free addition ultra-thin high density fiberboard.
The following preparation process of the zero-aldehyde added ultrathin high-density fiberboard is as follows:
s1: a wood chip treatment process: peeling the raw wood, and chipping the wood raw material into wood chips with the length of 3cm, the width of 25cm and the thickness of 1.5cm by a chipping machine. Preheating the wood chips in a preheating bin at 95 deg.c and 170 deg.c and steaming pressure of 8.0bar for 2.5 min;
s2: a fiber preparation process: the wood chips enter a defibrator through a belt type screw, the gap between grinding discs is controlled to be 0.25mm, the length of the prepared wood fiber is 3mm, and the length-width ratio is 65;
s3: sizing: pumping component A into the inlet of the spraying pipe via a sizing pump, pumping component B into the inlet of the spraying pipe via another sizing pump, spraying component A and component B onto the fiber via a high pressure nozzle, and mixing with the fiber uniformly, wherein the application amount of the composite material is 40Kg/m3；
S4: and a drying procedure, namely drying for 10s after sizing, and controlling the water content of the raw material to be 10 wt%.
S5: a sorting step of removing foreign matters such as lumps, fiber clusters, fiber bundles and the like;
s6: a paving prepressing procedure, wherein fibers are paved through a plurality of groups of leveling rollers, then slab prepressing is carried out at the pressure of 15MPa, and trimming is carried out on the slabs;
s7: and (3) a hot pressing process, wherein the hot pressing temperature is 230-160 ℃, a five-section hot pressing temperature area is adopted, the hot pressing pressure is 0-40 MPa, and the hot pressing speed is as follows: 200 m/min;
s8: and (5) post-treatment, cooling and curing for 72h, and sawing. The ultrathin plate production line does not need a plate turning cold press, and hot-pressed plates are sawed into plain plates with specification and size.
The test results of the examples and comparative examples are shown in Table 1.
TABLE 1
The above test is with reference to the standard: Q/SLMY-01-2016 ultrathin high-density fiberboard
From the above examples and comparative examples, it was found that it is difficult to obtain good initial adhesion and initial strength of a slab by simply adding a polyisocyanate adhesive or a polyurethaneurea dispersion, and further, the slab cannot pass through a gap in high-speed operation, resulting in production interruption. Meanwhile, the polyisocyanate and the polyurethane urea dispersoid are added, so that the continuous industrial production is realized, and the good performance is obtained, and the requirement of the market at the present stage on the ultrathin high-density fiberboard can be met.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (20)
1. An aqueous polyurethane urea dispersion obtained by reaction of at least the following components:
a) at least one polyurea polyol having a number average molecular weight Mn of not less than 500 and not more than 3000g/mol, a hydroxyl functionality of not less than 1.5 and not more than 4 and containing one or more hydrophilic compounds of ionic groups, potentially ionic groups and non-ionic groups;
b) at least one polyester polyol;
c) at least one isocyanate;
d) at least one hydrophilic compound containing one or more of an ionic group, a potentially ionic group and containing 2-3 NCO-reactive functional groups;
e) optionally blocking agents for isocyanate groups.
2. The aqueous polyurethane urea dispersion according to claim 1, wherein the following components are used, based on 100 parts by weight of the total amount of components a) to e):
10-85 parts by weight of component a);
the component b) is 7 to 30 weight parts;
the component c) is 5 to 40 weight parts;
0.3 to 10 parts by weight of component d);
the component e) is 0 to 15 parts by weight.
3. The aqueous polyurethane urea dispersion according to claim 2, wherein the following components are used, based on 100 parts by weight of the total amount of components a) to e):
component a) is 40-70 parts by weight;
10-30 parts by weight of component b);
the component c) is 15 to 30 parts by weight;
0.3 to 5 parts by weight of component d);
the component e) is 0 to 8 parts by weight.
4. The aqueous polyurethaneurea dispersion of claim 1 or claim 2, wherein the component polyurea polyol of a) is selected from one or more of the compounds represented by the following structural formula:
in the formula, R1Alkoxy selected from C1-C14;
R2alkylene with carboxyl, carboxylate or sulfonic acid group and sulfonate selected from C1-C10, cycloalkyl with carboxyl, carboxylate or sulfonic acid group and sulfonate with C7-C16, or ether group with carboxyl or sulfonic acid side group with C3-C16;
R3is selected from C1-C10 alkylene.
5. The aqueous polyurethane urea dispersion according to claim 4, wherein R is R1Alkoxy selected from C3-C14; r2Alkylene with carboxyl, carboxylate or sulfonic acid group and sulfonate selected from C3-C10, or cycloalkyl with carboxyl, carboxylate or sulfonic acid group and sulfonate selected from C7-C10; r3Is- (CH)2)6-。
6. The aqueous polyurethane urea dispersion according to claim 5, wherein R is R1Is selected from CH3(CH2)3O-、CH3(CH2)7O-、CH3CH(CH3)O-、CH3(CH2)11O-、CH3(CH2)12O-or CH3(CH2)13O-；R2Is selected from
7. The aqueous polyurethane urea dispersion according to any of claims 1 to 3, characterised in that the component b) polyester polyol is selected from one or more of the group consisting of polyester polyols having a Mn of 1000-10000g/mol and a functionality of 2-4.
8. The aqueous polyurethane urea dispersion according to claim 7, wherein the component b) polyester polyol is selected from one or more of the group consisting of polyester polyols having a Mn of 1000-3000g/mol and a functionality of 2-4.
9. The aqueous polyurethane urea dispersion according to claim 8, wherein the component b) polyester polyol is selected from one or more of polycaprolactone diol, polycarbonate diol, polyethylene adipate diol, poly-1, 4-butanediol adipate diol, poly-neopentyl glycol adipate diol, poly-1, 6-hexanediol adipate diol, and poly-1, 6-hexanediol adipate diol.
10. The aqueous polyurethane urea dispersion according to any one of claims 1 to 3, characterised in that the isocyanate of component c) is selected from one or more of aliphatic isocyanates, cycloaliphatic isocyanates and aromatic isocyanates.
11. The aqueous polyurethane urea dispersion according to claim 10, wherein the isocyanate component c) is selected from one or more of the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate trimer, dodecamethylene diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate.
12. The aqueous polyurethane urea dispersion according to any one of claims 1 to 3, characterised in that the component d) is selected from one or more of the group consisting of diamino sulfonic acids and salts thereof, diamino carboxylic acids and salts thereof, dihydroxy sulfonic acids and salts thereof.
13. The aqueous polyurethane urea dispersion according to claim 12, characterised in that the component d) is selected from one or more of diaminocyclohexanecarboxylic acid, N- (2-aminoethyl) -2-aminoethanesulphonic acid and its alkali metal and/or ammonium salts, N- (3-aminopropyl) -3-aminopropanesulphonic acid and its alkali metal and/or ammonium salts and N- (2-aminoethyl) -3-aminopropanesulphonic acid and its alkali metal and/or ammonium salts.
14. The aqueous polyurethane urea dispersion according to any of claims 1 to 3, characterised in that component e) is selected from one or more of methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-N-propylamine, morpholine, piperidine, 2-amino-2-methyl-1-propanol and diethanolamine.
15. The aqueous polyurethane urea dispersion according to claim 14, wherein component e) is diethanolamine.
16. An adhesive composition comprising a polyisocyanate and the polyurethaneurea dispersion of any one of claims 1-15, wherein the polyisocyanate is present in an amount of 95-99.5% by weight based on the solid mass of the adhesive composition.
17. The adhesive composition according to claim 16, wherein the polyisocyanate accounts for 98-99% of the solid mass of the adhesive composition.
18. The adhesive composition of claim 16, wherein the polyisocyanate is polymethylene polyphenyl polyisocyanate and/or its derivatives.
19. The adhesive composition of claim 18, wherein the polyisocyanate is polymethylene polyphenyl polyisocyanate having NCO% of 29-35% and viscosity of 150-250cp (25 ℃), and/or a derivative thereof.
20. The adhesive composition according to any one of claims 16 to 19 is applied to the preparation of a zero-aldehyde-added ultrathin high-density fiberboard.
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| DE2555534C3 (en) * | 1975-12-10 | 1981-01-08 | Bayer Ag, 5090 Leverkusen | Polyurethanes dispersible in water |
| DE102005040130A1 (en) * | 2005-08-25 | 2007-03-01 | Bayer Materialscience Ag | Polyurethane polyurea dispersions |
| CA3027638A1 (en) * | 2016-06-30 | 2018-01-04 | Covestro Deutschland Ag | Adhesive based on a special polyurethane urea, and production and use thereof |
| CN107955126B (en) * | 2017-12-01 | 2020-08-28 | 万华化学（宁波）有限公司 | Aqueous dispersion of polyurethane-polyurea polyol and preparation method thereof |
| CN109942787B (en) * | 2017-12-21 | 2021-04-20 | 万华化学（宁波）有限公司 | Polyurethane-polyurea aqueous dispersion, preparation method thereof and application thereof in waterborne wood coating |
| JP2021507040A (en) * | 2017-12-21 | 2021-02-22 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Adhesives with adjustable adhesive strength based on a special polyurethane urea, its manufacture and use |
| CN109081897A (en) * | 2018-08-01 | 2018-12-25 | 万华化学集团股份有限公司 | The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application |
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