CN102485448A - Environment-friendly type artificial board and preparation method thereof - Google Patents

Abstract

The invention provides an environment-friendly type artificial board and a preparation method thereof, which relate to the field of artificial boards. The raw materials of the environment-friendly type artificial board contain an adhesive and a scrap material of the artificial board. The adhesive comprises isocyanate and a water-soluble polyester water solution; the content of the isocyanate is 25 to 150 parts calculated by taking the water-soluble polyester water solution as 100 parts by weight; and the content of water-soluble polyester in the water-soluble polyester water solution is 10 to 40wt%. The water-soluble polyester contains a hydrophilic monomer selected from isophthalic acid-5-sulphonate or a derivative thereof, and the content of the monomer is 5 to 20mol% of the mole number of dicarboxylic acid in the water-soluble polyester; the water-soluble polyester contains a branched polyhydric alcohol component of which the degree of functionality is greater than 2, and the content of the component is 0.3 to 3.0mol% of the mole number of the dicarboxylic acid; and the specific viscosity of the water-soluble polyester is 0.25 to 0.50dL/g. The isocyanate in the adhesive accounts for 2.0 to 8wt% of the dry weight of the scrap material of the artificial board. The artificial board has the function of protecting the environment and has good mechanical property.

Description

A kind of environment friendly artificial board and preparation method thereof

Technical field

The present invention relates to the wood-based plate field, particularly relate to a kind of environment friendly artificial board and preparation method thereof.

Background technology

The adhesive of producing the wood-based plate employing at present mainly is three aldehyde adhesives; Be Lauxite, phenolic resins, melamine resin adhesive; These adhesives are in glue and pressing plate process; And in use having formaldehyde to overflow with the wood-based plate of three-aldehyde glue production, contaminated air is detrimental to health.

The raising of Along with people's quality of life, people press for the environment friendly artificial board of formaldehydeless effusion, press for to use no aldehyde environment-friendly adhesive to replace three aldehyde adhesives.

At present commonly used, effect adhesive without aldehyde preferably is the isocyanates adhesive; This adhesive has that bond properties is good, the advantage of the formaldehydeless harm of goods; But in the pressing plate production process; Because existing adhesive applying glue difficulty, uniformity of size application are poor, cause that binder dosage is big, production cost is high.

One Chinese patent application CN101760159A (application number 201010104199.4) " a kind of formaldehydeless adhesion agent for artificial board and preparation method thereof " provides a kind of formaldehydeless adhesion agent for artificial board and preparation method thereof: with self-crosslinking acrylic resin soap-free emulsion, calcium carbonate, starch; After mixing with water; Add again after the water dispersible isocyanates mixes, promptly make formaldehydeless adhesion agent for artificial board.This method adopts the water dispersible isocyanates, and isocyanates is difficult in water, disperse usually, need carry out modification to isocyanates.

Chinese patent CN1524669A (application number 03143307.3) " zero-formaldehyde particleboard and working method " provides a kind of zero-formaldehyde particleboard and working method, is characterized in using many benzene of polymethylene polyisocyanates (PAPI) and isocyanates water soluble adhesive.But the component of isocyanates water soluble adhesive is not announced in this patent application.

One Chinese patent application CN101254608A (application number 200810027452.3) " a kind of environment-friendly type shaving board and production method thereof " discloses a kind of environment-friendly type shaving board and production method thereof, and characteristics are that string base polyester ether polylol and isocyanates are mixed into adhesive.

One Chinese patent application CN101314235A (application number 200810050827.8) " aqueous macromolecule-isocyanic ester stalk artificial board and preparation method thereof " is used for the production of artificial board of straw with aqueous macromolecule-isocyanate glue instead of pure isocyanate glue.Wherein aqueous high molecular complex emulsions, binary acid esterification agent, polyvinyl alcohol, the anticorrisive agent be made up of modified starch and styrene-butadiene latex or ethylene-acetate ethyl ester emulsion or benzene emulsion of aqueous high molecular formed.The composition of this adhesive is complicated.

One Chinese patent application CN1884414A (application number 200510050471.4) " aldehyde-free cement for wood-based panel " discloses a kind of aldehyde-free cement for wood-based panel; It is made up of polyvinyl alcohol, YH-complexing agent, starch, BPA crosslinking agent; Warp heats up, insulation reaction is prepared into host, is curing agent with the polyisocyanates.Host and curing agent isocyanates are mixed with aldehyde-free cement according to a certain percentage.But this adhesive is formed complicated.

Summary of the invention

Problem to the prior art existence; Through isocyanates being used to produce the experimental study of wood-based plate; We find that isocyanates can well be dispersed in a kind of aqueous solution of water-soluble polyester, thereby well solve the problem of the uniformity of size application of isocyanates in Wood-based Panel Production.Through the chemical reaction of water-soluble polyester active group and isocyanates, improve the adhesive property of adhesive, improve the intensity of wood-based plate; Reduce adhesive use amount and production cost simultaneously.

So one of the object of the invention provides a kind of environment friendly artificial board.This environment friendly artificial board is formaldehydeless, and is pollution-free, and mechanical property is good, durable in use.

Concrete technical scheme of the present invention is following:

A kind of environment friendly artificial board of the present invention, its raw material packet contains following component: adhesive and wood-based plate bits material.

Wherein said wood-based plate bits material is for wood-based plate bits material commonly used in the prior art, like wood chip, brush wood, cotton stalk, rice straw, wheat straw stalk etc.

Wherein said adhesive comprises the aqueous solution of isocyanates and water-soluble polyester.

When said adhesive in preparation during wood-based plate, if isocyanate content is too high, under the situation of using identical amount of isocyanate, the adhesive total amount of use is very few, the isocyanates in the adhesive then is difficult for being uniformly dispersed in wood-based plate bits material; Corresponding water-soluble poly ester content tails off relatively, makes the crosslinking points of adhesive few, influences the performance of wood-based plate.Isocyanate content is low excessively, and total use amount of adhesive is excessive, possibly cause in the applying glue raw material moisture excessive.So the content of isocyanates is 100 parts by weight in the aqueous solution of water-soluble polyester described in the adhesive of the artificial plate bits of the present invention material, is 25～150 parts, is preferably 40～125 parts.

When said adhesive in preparation during wood-based plate, according to the requirement of device to water content in the raw material after the applying glue, the optional 10～40%wt of weight content of water-soluble polyester in the said water-soluble poly aqueous solution of ester, preferred 20～35%wt.The water-soluble poly ester content is too low, will cause in the adhesive crosslinking points of water-soluble polyester and isocyanates few, and the active constituent content of adhesive is few simultaneously, makes the mechanical properties decrease of wood-based plate.The too high levels of water-soluble polyester in the water-soluble poly aqueous solution of ester, viscosity in aqueous solution is excessive, water-soluble the separating and the dispersion of isocyanates that is unfavorable for water-soluble polyester.

Wherein said isocyanates plays adhesive effect in adhesive, the hydroxyl reaction during its adhesive effect is expected through isocyanates and water-soluble polyester, water, wood-based plate bits takes place to solidify to be realized.Said isocyanates is a disclosed isocyanates in the prior art, be to improve adhesion strength, and preferred degree of functionality is greater than 2 polyisocyanates.Isocyanates among the present invention can be preferably at least a in the following concrete material: toluene di-isocyanate(TDI), diphenyl methane-4; 4 '-vulcabond, 1; Hexamethylene-diisocyanate, XDI, naphthalene-vulcabond, poly methylene poly phenyl poly isocyanate, polymeric isocyanate, triphenylmethane triisocyanate.Wherein more preferred like the polyisocyanates of poly methylene poly phenyl poly isocyanate, polymeric isocyanate, triphenylmethane triisocyanate etc.

Isocyanates weight accounts for 2.0～8%wt of wood-based plate bits material dry weight in the wherein said adhesive, is preferably 2.5～6.0%wt.

Water-soluble polyester described in the prior art is meant that by dicarboxylic acids, dihydroxylic alcohols be base stock, and adds solubilized in water or dispersible polyester that hydrophilic monomer is polymerized.Water-soluble polyester needs the active group that curing reaction can take place with isocyanates described in the adhesive of the artificial board raw material of the present invention.And the inherent viscosity of said water-soluble polyester also has certain requirement, and its inherent viscosity is too small, and the molecular weight of product is too little, and active group is more relatively, and is big with the reactivity of isocyanates, influences the storage period of adhesive; Its inherent viscosity is excessive, and the water-soluble that influences polyester product can; Because molecular weight is too big, active group is less relatively, and is few with the crosslinking points of isocyanate reaction, influences the mechanical property of wood-based plate simultaneously.The active group of the water-soluble polyester in the adhesive according to the invention mainly is a terminal hydroxy group.Terminal hydroxy group can with isocyanate groups generation curing reaction.Therefore, water-soluble polyester according to the invention can with isocyanates generation curing reaction, with isocyanates good compatibility is arranged, isocyanates is uniformly dispersed in the aqueous solution of this water-soluble polyester easily.Therefore can cooperate isocyanates to form the artificial board adhesive of no aldehyde environmental protection, make the adhesive applying glue easy and even, reduce cost thereby save binder dosage.This water-soluble polyester can also react with isocyanates in the pressing plate process of making wood-based plate, increases the crosslinking degree of isocyanates, improves the mechanical property of wood-based plate.

Said water-soluble polyester adopts dicarboxylic acids, dihydroxylic alcohols and hydrophilic monomer to form for the base stock copolymerization.

The degree of functionality that said water-soluble polyester also contains branching is greater than 2 polyol component.Said degree of functionality is to make polyester produce branching active group, the i.e. terminal hydroxy group of branching greater than the effect of 2 polyalcohol.This group can with the isocyanate reaction in the said adhesive, increase the crosslinking degree of polyester and isocyanates, thereby make the adhesive applying glue easily and evenly, and in the application of making wood-based plate the mechanical property of raising wood-based plate.Degree of functionality can be selected in the prior art at least a in the existing polyalcohol for use greater than 2 polyalcohol, at least a in preferred trihydroxylic alcohol, the tetrahydroxylic alcohol, at least a as in glycerine, orthoformic acid, the pentaerythrite etc.Its addition is 0.3～3%mol of dicarboxylic acids integral molar quantity, preferred 0.5～2.0%mol.Addition is too small, and the branching amount is too little, and is not obvious to the mechanical property raising of wood-based panel product; The branching amount is too big, and crosslinking degree own is big in the polyester manufacture process, is unfavorable for the preparation of polyester.

Hydrophilic monomer in the said water-soluble polyester is selected from M-phthalic acid-5-sulfonate or derivatives thereof, is the main group that makes the polyester possess hydrophilic property.At least a in preferred 5-sodium sulfo isophthalate, M-phthalic acid-5-sulfonic acid lithium, the 5-sodium sulfo isophthalate glycol ester (SIPE).The hydrophilic monomer addition is too small, polyester water-soluble influenced; Addition is excessive, and the cost of product increases.Its addition is preferably 5～20%mol of dicarboxylic acids integral molar quantity, more preferably 8～16%mol.In polyester production process, for ease of polyester manufacture, 5-sodium sulfo isophthalate glycol ester (SIPE) most preferably.

Dicarboxylic acids in the said water-soluble polyester is selected from existing dicarboxylic acids in the prior art, preferably from least a in terephthalic acid (TPA), adipic acid, decanedioic acid, the M-phthalic acid etc.Said dicarboxylic acids more preferably comprises terephthalic acid (TPA) and other dicarboxylic acids.If the content of other binary acid is excessive, cause the product fusing point low excessively.Because fusing point is low excessively, the difficult slivering of material bar causes tie rod discharging difficulty easily, so other dicarboxylic acids except that terephthalic acid (TPA) better are no more than dicarboxylic acids total amount 30mol%, preferably is no more than 20mol% in the discharging process.That is to say that the content of terephthalic acid (TPA) preferably accounts for the 70mol% of total amount at least in the said dicarboxylic acids, preferably account for 80mol% at least.Said dicarboxylic acids optimum is a terephthalic acid (TPA).

Dihydroxylic alcohols in the said water-soluble polyester is selected from existing dihydroxylic alcohols in the prior art, preferably from least a in ethylene glycol, propane diols, the butanediol.Said dihydroxylic alcohols more preferably comprises ethylene glycol and other dihydroxylic alcohols.The content of other dihydroxylic alcohols is excessive, can cause the product fusing point low excessively, causes the discharging difficulty, so other dihydroxylic alcohols except that ethylene glycol better are no more than dihydroxylic alcohols total amount 40mol%, preferably is no more than 30mol%.That is to say that glycol content in the said dihydroxylic alcohols preferably accounts for the 60mol% of total amount at least, preferably accounts for 70mol% at least.Said dihydroxylic alcohols optimum is an ethylene glycol.

Dicarboxylic acids, dihydroxylic alcohols, polyalcohol are preferably 1.2～1.5 by alcohol and sour mol ratio in the said water-soluble polyester.

If the water-soluble polyester inherent viscosity in the said adhesive is too small, the molecular weight of product is too little, and active group is more relatively, and is big with the reactivity of isocyanates, can the storage period of adhesive be exerted an influence; Its inherent viscosity is excessive, can exert an influence to the water-soluble of polyester product; Because molecular weight is too big, and active group is less relatively, and is few with the crosslinking points of isocyanate reaction, also can produce some influences simultaneously to the mechanical property of wood-based plate.So the preferable range of the inherent viscosity of water-soluble polyester is at 0.25～0.50dL/g described in the adhesive of the artificial plate bits of the present invention material.Said inherent viscosity is measured according to the method for GB/T 14190-2008.

Water-soluble polyester described in the adhesive has well water-soluble, in the hot water more than 90 ℃, stirs, and can dissolve fully in 30 minutes.Reduce to normal temperature after the dissolving and do not separate out, its water-soluble fluid power long-term stability is deposited.This water-soluble polyester and isocyanates have good compatibility, and isocyanates is uniformly dispersed in the aqueous solution of water-soluble polyester easily.This water-soluble polyester can react with isocyanates in the pressing plate process of making wood-based plate simultaneously, increases the crosslinking degree of isocyanates, improves the mechanical property of wood-based plate.

The effect that water-soluble polyester plays in the adhesive: (1) can be miscible with isocyanates, increases the applying glue convenience; (2) terminal hydroxy group of water-soluble polyester can and isocyanate reaction; (3) terminal hydroxy group of branching and isocyanate reaction increase the degree of cross linking, thereby increase the particieboard mechanical property.

Can to select existing inherent viscosity in the prior art for use be 0.25～0.50dL/g and the degree of functionality that contains 0.3～3.0mol/% branching to the said water-soluble polyester of adhesive greater than the water-soluble polyester of 2 polyalcohol monomer in the artificial board raw material of the present invention.Above-described water-soluble polyester also can be by following method preparation.The preparation method of conventional water-soluble polyester is identical in processing step in its preparation method and technological parameter condition and the prior art, comprises esterification, copolyreaction.

Furtherly, be with comprising dicarboxylic acids, dihydroxylic alcohols, said degree of functionality component, and hydrophilic monomer obtain described water-soluble polyester through esterification, copolymerization greater than 2 polyalcohol.Be about to dicarboxylic acids, dihydroxylic alcohols, degree of functionality and join the making beating still greater than 2 polyalcohol etc., add polyester catalyst, stabilizing agent simultaneously, making beating evenly together; Get into the esterifying kettle esterification afterwards continuously.Carboxylate is pressed into polymeric kettle, adds hydrophilic monomer, and the polycondensation reaction of pressing normal polyester then vacuumizes polymerization and makes the water-soluble polyester product.The process conditions of esterification, copolymerization are like temperature, stress reaction time etc., all identical with technology of the prior art.

Specifically, the preparation method of said water-soluble polyester can may further comprise the steps:

(1) will comprise that polyester catalyst, stabilizing agent and said dicarboxylic acids, dihydroxylic alcohols, degree of functionality put into the making beating still together greater than the component of 2 polyalcohol and stir; Get into the esterifying kettle esterification then continuously.

Above-mentioned esterification reaction temperature, pressure, termination condition are routine.Esterification generally is the standard that reaction finishes with the water yield in the actual production.The 95%wt that general water yield surpasses in the theoretical water yield of material quantity can finish reaction.Play the catalyst of catalytic action when wherein polyester catalyst is polycondensation, generally select antimony oxide, antimony glycol; Consumption is conventional.Stabilizing agent is a stabilizing agent used in the normal polyester technology, generally selects Phosphorus compound for use; Consumption is conventional.

(2) after esterification finished, carboxylate was pressed into polymeric kettle, adds the ethylene glycol solution of said hydrophilic monomer, carries out polycondensation after stirring, and prepares said water-soluble polyester.

Hydrophilic monomers content is common content in the ethylene glycol solution of said hydrophilic monomer, generally can be 20～40%wt.

Mixing time in the said step (2) before the polycondensation generally more fortunately 30 minutes or more than.The temperature and pressure condition of said polycondensation reaction is with the temperature and pressure condition of polyester polycondensation reaction in the prior art.

In order to improve the viscosity of adhesive in the artificial plate of the present invention, make its application that adapts to various Wood-based Panel Production, wherein can also contain components such as cellulose or polyvinyl alcohol, can be used to improve the viscosity of adhesive.Wherein cellulosic content is 0～2.0%wt of adhesive gross weight, and the content of polyvinyl alcohol is 0～5.0%wt of adhesive gross weight.

Two of the object of the invention provides the preparation method of said environment friendly artificial board.

Environment friendly artificial board of the present invention can be by the applying glue and the pressing plate technology of existing artificial plate production, and according to the resin added requirement, adding described adhesive also, pressing plate prepares.

Specifically, adhesive according to the invention and wood-based plate bits material is mixed, through the method for existing manufacturing wood-based plate, comprise mat formation, the step of precompressed, hot pressing, side cut makes environment friendly artificial board.The pulverizing of described wood-based plate bits material, mat formation, precompressed, heat pressing process adopt existing Wood-based Panel Production technology.

According to the requirement to the wood-based plate mechanical property, the use amount of said adhesive is 2.0～8%wt that isocyanates weight accounts for wood-based plate bits material dry weight in the adhesive, preferred 2.5～6.0%wt.Addition is low excessively, and the mechanical property of wood-based plate is low.Addition is too high, though the mechanical property of wood-based plate is very high, production cost is high.Prepare in addition in the raw material of environment friendly artificial board and also can include the conventional auxiliary agent that is used for wood-based plate in the prior art, like waterproofing agent (paraffin) etc., consumption also is conventional.

The adhesive of the artificial board raw material of the present invention mixes components such as isocyanates and water-soluble poly aqueous solution of ester by said amount and to obtain in the preparation.The preparation method of adhesive of the present invention specifically may further comprise the steps:

(1) earlier said water-soluble polyester is dissolved in the aqueous solution of processing polyester in the water by said amount;

(2) then, the above-mentioned polyester aqueous solution is mixed by said amount with said isocyanates, obtain said adhesive after stirring.Wherein, can add components such as cellulose or polyvinyl alcohol and adjust according to the viscosity needs of adhesive.

More specifically, the preparation of water-soluble poly aqueous solution of ester comprises: water-soluble polyester is ground into the particle below the diameter 5mm with pulverizer earlier.In the container that has stirring and heating system, add entry and water-soluble polyester particle, under stirring, be heated to more than 90 ℃ and maintenance, dissolve fully, stir then and cool to normal temperature, obtain the aqueous solution of water-soluble polyester up to polyester granulate.The water-soluble poly ester content is 10～40%wt in this solution, preferred 20～35%wt.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Under the normal temperature, water-soluble polyester of the present invention and isocyanate reaction are not obvious, and should be able to deposit more than 4 hours after the mixing does not have significant change.

Because each component of said adhesive in use is that existing usefulness is joined at present; Isocyanates and water-soluble polyester mix and begin to react after back four hours in the adhesive; So the resting period for preparing before use the back at adhesive of the present invention should be less than 4 hours, most preferably less than 3 hours.

Environment friendly artificial board of the present invention does not contain formaldehyde, component is simple, mechanical property good, durable in use.Applying glue is convenient when producing wood-based plate, and adhesive mixes easy and uniform with wood-based plate bits material, prepares simply.

The specific embodiment

The adhesive of environment friendly artificial board of the present invention is mixed by said consumption by isocyanates and water-soluble poly aqueous solution of ester.Can contain cellulose or polyvinyl alcohol in the water-soluble poly aqueous solution of ester as required.The mating formation of Wood-based Panel Production, precompressed, heat pressing process adopt existing Wood-based Panel Production technology.Preparation embodiment through water-soluble polyester, adhesive and the environment friendly artificial board mentioned among the present invention is to further explain of the present invention below.

Testing standard: the particieboard performance measurement is undertaken by GB/T 17657-1999.

Raw material:

Isocyanates: PM200, polymeric isocyanate, Yantai Wanhua Polyurethane Co., Ltd.

Terephthalic acid (TPA), M-phthalic acid, ethylene glycol, 1,4-butanediol, pentaerythrite, glycerine, antimony oxide, trimethyl phosphate, 5-sodium sulfo isophthalate glycol ester (SIPE), cellulose (CMC) all can be commercially available and be got.

First group:

One, the water-soluble polyester and the aqueous solution thereof preparation

Embodiment 1: the preparation of water-soluble polyester 1 and this water-soluble poly aqueous solution of ester 1A

With terephthalic acid (TPA) 1660g (10mol), ethylene glycol 806g (13mol), glycerine 10.3g (0.112mol), polyester catalyst antimony oxide 0.54g, stabilizing agent trimethyl phosphate 0.4g, put into the making beating still and stir together.Get into esterifying kettle then continuously, esterification under 250～260 ℃ of temperature, esterification water outlet 360g (theoretical water yield is more than 95%) reacts end.Carboxylate is pressed into polymeric kettle, adds the ethylene glycol solution 1214g (SIPE is 1.2mol) that contains 35%wtSIPE, stirs 30 minutes; In low vacuum; 240～270 ℃ of following precondensation of temperature, in the high vacuum less than 200Pa, 270～280 ℃ of following polycondensation dischargings of temperature get water-soluble polyester 1.This water-soluble polyester inherent viscosity is 0.40dL/g.

With pulverizer this water-soluble polyester is ground into the particle below the diameter 5mm.In the container that has stirring and heating system, add entry 70g; The particle 30g of water-soluble polyester 1 stirs and is heated to more than 90 ℃ and maintenance, dissolves fully with endoparticle in 20 minutes; Stirring cools to the aqueous solution 1A that normal temperature obtains this polyester, water-soluble poly ester content 30%wt.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 2: the preparation of water-soluble polyester 2 and this water-soluble poly aqueous solution of ester 2A

Reference implementation example 1.Different is the mixture replacement of terephthalic acid (TPA) 10mol with terephthalic acid (TPA) 9mol and M-phthalic acid 1mol, according to the method for embodiment 1, and preparation water-soluble polyester 2, product performance viscosity is 0.41dL/g

The polyester aqueous solution 2A (water-soluble poly ester content 30%wt) of this polyester of method dissolving of reference implementation example 1.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 3: the preparation of water-soluble polyester 3 and this water-soluble poly aqueous solution of ester 3A

Reference implementation example 1.Different is the pentaerythrite replacement of glycerine 0.112mol with 0.06mol, according to the method for embodiment 1, and preparation water-soluble polyester 3, product performance viscosity is 0.39dL/g.

This polyester of method dissolving of reference implementation example 1 must this polyester aqueous solution 3A (water-soluble poly ester content 30%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 4: the preparation of water-soluble polyester 4 and this polyester aqueous solution 4A

Reference implementation example 1.Change the actual addition of SIPE ethylene glycol solution into 1821g (SIPE is 1.8mol), according to the method for embodiment 1, preparation water-soluble polyester 4, product performance viscosity is 0.34dL/g.

This polyester of method dissolving of reference implementation example 1 must this polyester aqueous solution 4A (water-soluble poly ester content 30%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 5:The preparation of water-soluble polyester 5 and this polyester aqueous solution 5A

Reference implementation example 1.Change the actual addition of SIPE ethylene glycol solution into 810g (SIPE is 0.8mol), according to the method for embodiment 1, preparation water-soluble polyester 5, product performance viscosity is 0.45dL/g.

This polyester of method dissolving of reference implementation example 1 must this polyester aqueous solution 5A (water-soluble poly ester content 30%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 6: the preparation of water-soluble polyester 6 and this water-soluble poly aqueous solution of ester 6A

Reference implementation example 1.Different is that dihydroxylic alcohols adopts ethylene glycol 744g (12mol), 1, and the mixture of 4-butanediol 135g (1.5mol) replaces, according to the method for embodiment 1, and preparation water-soluble polyester 6, product performance viscosity is 0.43dL/g

The polyester aqueous solution 6A (water-soluble poly ester content 30%wt) of this polyester of method dissolving of reference implementation example 1.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Embodiment 7: the preparation of water-soluble polyester 7 and this water-soluble poly aqueous solution of ester 7A

Reference implementation example 1.With terephthalic acid (TPA) 1660g (10mol), ethylene glycol 682g (11mol), 1; 4-butanediol 135g (1.5mol), glycerine 23g (0.25mol), polyester catalyst antimony oxide 0.54g, stabilizing agent trimethyl phosphate 0.4g put into the making beating still and stir together.Get into the esterifying kettle esterification then continuously.Carboxylate is pressed into polymeric kettle, adds the ethylene glycol solution 1012g (SIPE is 1.0mol) that contains 35%wtSIPE, stirs 30 minutes, and polymerization gets water-soluble polyester 7 then.This water-soluble polyester inherent viscosity is 0.37dL/g.

The polyester aqueous solution 7A (water-soluble poly ester content 30%wt) of this polyester of method dissolving of reference implementation example 1.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Comparative example 1: the preparation of water-soluble polyester 8

Reference implementation example 1.Change the actual addition of SIPE ethylene glycol solution into 405g (SIPE is 0.4mol), according to the method for embodiment 1, preparation water-soluble polyester 9, product performance viscosity is 0.43dL/g.

With pulverizer this polyester is ground into the particle below the diameter 5mm.In the container that has stirring and heating system, add entry 70g, polyester granulate 30g is heated to more than 90 ℃ and maintenance, and particle can not dissolve fully in 2 hours.Owing to can not dissolve fully, can not obtain the polyester dispersion liquid, can not use.

Comparative example 2: the preparation of water-soluble polyester 10 and this polyester aqueous solution 10A

Reference implementation example 1.The addition that will contain the ethylene glycol solution of 35%SIPE changes 3540g (3.5mol) into, according to the method for embodiment 1, and preparation water-soluble polyester 10.Product performance viscosity is 0.33dL/g.

With pulverizer this polyester is ground into the particle below the diameter 5mm.In the container that has stirring and heating system, add entry 70g, polyester granulate 30g, stirring is heating down, is warmed up to 70 ℃ of particles and dissolves fully.Stirring cools to the aqueous solution 10A (water-soluble poly ester content 30%wt) that normal temperature obtains this polyester.The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.Because the SIPE addition is too big, under the same viscosity number, the molecular weight of water-soluble polyester is little.

Comparative example 3: the preparation of water-soluble polyester 11 and this polyester aqueous solution 11A

Reference implementation example 1.The control polycondensation time, make that water-soluble polyester 11 inherent viscosities of discharging are 0.20dL/g.This polyester intensity is very low.

The dissolving method of reference implementation example 1 is prepared into this polyester aqueous solution 11A (water-soluble poly ester content 30%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Comparative example 4: the preparation of water-soluble polyester 12 and this polyester aqueous solution 12A

Reference implementation example 1.Prolong polymerization time, make that water-soluble polyester 12 inherent viscosities of discharging are 0.55dL/g.

The dissolving method of reference implementation example 1 is prepared into modification of (co) polyesters aqueous solution 12A (water-soluble poly ester content 30%wt).This polyester aqueous solution is deposited after 12 days and lamination occurred.

Comparative example 5: the preparation of water-soluble polyester 13 and this polyester aqueous solution 13A

Reference implementation example 1.Different is that the glycerine consumption is 1.84g (0.02mol), according to the method for embodiment 1, and preparation water-soluble polyester 13, product performance viscosity is 0.41dL/g.

This polyester of method dissolving of reference implementation example 1 must this polyester aqueous solution 13A (water-soluble poly ester content 30%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

Comparative example 6: the preparation of water-soluble polyester 14

Reference implementation example 1.Different is that the glycerine consumption is 46g (0.5mol), and the method operation according to embodiment 1 gets into the high vacuum later stage; Because the polyalcohol consumption is big, and causes the crosslinked polymer degree big, thereby viscosity is excessive; Make and stir difficulty, the stir current of polymeric kettle rises very fast, pauses a little; Because stir current rises to and can not stir, and uses nitrogen pressure, because the too big discharging difficulty of viscosity.

Two, wood-based plate (particieboard) preparation

Embodiment 8: do adhesive component with polyester aqueous solution 1A and prepare particieboard

In having the container of stirring, adding PM200 is 100g, the water-soluble poly aqueous solution of ester 1A100g of 30%wt, and stirring obtains adhesive 1.PM200 is that 100 weight portions are counted 100 parts with the water-soluble poly aqueous solution of ester in the said adhesive 1, and PM200 is the 50%wt of adhesive gross weight, and water-soluble polyester is the 15%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

Press the particieboard production technology; The 80g of adhesive 1 is joined (PM200 and water-soluble polyester be 52g altogether, and PM200 accounts for the 4.0%wt of wood shavings amount) in the 1000g wood shavings, stir; Through mat formation, precompressed, hot pressing, side cut, sanding make the environmental protection particieboard that thickness is 16mm.190 ℃ of hot pressing temperatures, pressure 18Mpa, 7 minutes time.The particieboard performance is seen table 1.

Embodiment 9: do adhesive component with polyester aqueous solution 2A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 2A and obtain adhesive 2, and the preparation particieboard.The particieboard performance is seen table 1.

Embodiment 10: do adhesive component with polyester aqueous solution 3A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 3A and obtain adhesive 3, and the preparation particieboard.The particieboard performance is seen table 1.

Embodiment 11: do adhesive component with polyester aqueous solution 4A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 4A and obtain adhesive 4, and the preparation particieboard.The particieboard performance is seen table 1.

Embodiment 12: do adhesive component with polyester aqueous solution 5A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 5A and obtain adhesive 5, and the preparation particieboard.The particieboard performance is seen table 1.

Embodiment 13: do adhesive component with polyester aqueous solution 6A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 6A and obtain adhesive 6, and the preparation particieboard.The particieboard performance is seen table 1.

Embodiment 14: do adhesive component with polyester aqueous solution 7A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 7A and obtain adhesive 7, and the preparation particieboard.The particieboard performance is seen table 1.

Comparative example 7:10A does adhesive component with the polyester aqueous solution

Reference implementation example 8.Do adhesive component with polyester aqueous solution 10A and obtain contrasting adhesive 10.These adhesive 10 room temperatures are placed significant reaction were taken place in 2. hours 40 minutes.

Comparative example 8: 11A does adhesive component with the polyester aqueous solution

Reference implementation example 8.Do adhesive component with polyester aqueous solution 11A and obtain contrasting adhesive 11.These adhesive 11 room temperatures are placed significant reaction were taken place in 1.5 hours.

Comparative example 9: 12A does adhesive component with the polyester aqueous solution

Reference implementation example 8.Do adhesive component with polyester aqueous solution 12A and obtain contrasting adhesive 12, and the preparation particieboard.The particieboard performance is seen table 1.

Comparative example 10: do adhesive component with polyester aqueous solution 13A and prepare particieboard

Reference implementation example 8.Do adhesive component with polyester aqueous solution 13A and obtain contrasting adhesive 13, and the preparation particieboard.The particieboard performance is seen table 1.

Table 1:

Embodiment 15: do adhesive component with polyester aqueous solution 1A and prepare particieboard

With reference to embodiment 8: in having the container of stirring, adding PM200 is 60g, and the water-soluble poly aqueous solution of ester 1A of 30%wt is 140g, and stirring obtains adhesive 15.PM200 is that 100 weight portions are counted 43 parts with the water-soluble poly aqueous solution of ester in the said adhesive 15, and PM200 is the 30%wt of adhesive gross weight, and water-soluble polyester is the 21%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

Press the particieboard production technology; The 100g of adhesive 15 is joined (PM200 and water-soluble polyester be 51g altogether, and PM200 accounts for the 3.0%wt of wood shavings amount) in the 1000g wood shavings, stir; Through mat formation, precompressed, hot pressing, side cut, sanding make the environmental protection particieboard that thickness is 16mm.190 ℃ of hot pressing temperatures, pressure 18Mpa, 7 minutes time.The particieboard performance is seen table 2.

Embodiment 16:

With reference to embodiment 8, different is joins (PM200 and water-soluble polyester be 39g altogether, and PM200 accounts for the 3.0%wt of wood shavings amount) in the 1000g wood shavings with the 60g of adhesive 1.The particieboard performance is seen table 2.

Embodiment 17:

With reference to embodiment 8, different is joins (PM200 and water-soluble polyester be 78g altogether, and PM200 accounts for the 6.0%wt of wood shavings amount) in the 1000g wood shavings with the 120g of adhesive 1).The particieboard performance is seen table 2.

Embodiment 18:

With reference to embodiment 8, different is adds cellulose CMC again in the water-soluble poly ester concentration is the water-soluble poly aqueous solution of ester 1A of 30%wt, and the concentration of CMC in water-soluble poly aqueous solution of ester 1A is 1.5%wt.

In having the container of stirring, adding PM200 is 100g, above-mentioned water-soluble poly aqueous solution of ester 100g, and stirring obtains adhesive 18.PM200 content is 50%wt in the adhesive 18, and the water-soluble poly ester content is 15%wt, and CMC content is 0.75%wt.This adhesive room temperature is placed no significant change in 4 hours.

The 80g of adhesive 18 is joined (PM200 and water-soluble polyester be 52g altogether, and PM200 accounts for the 4.0%wt of wood shavings amount) in the 1000g wood shavings, press the identical prepared environmental protection particieboard of embodiment 8.The particieboard performance is seen table 2.

Embodiment 19:

The method dissolving water-soluble polyester 6 of reference implementation example 1 obtains polyester aqueous solution 19A (water-soluble poly ester content 20%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

With reference to embodiment 8: in having the container of stirring, adding PM200 is 100g, and the water-soluble poly aqueous solution of ester 19A of 20%wt is 100g, and stirring obtains adhesive 19.PM200 is that 100 weight portions are counted 100 parts with the water-soluble poly aqueous solution of ester in the said adhesive 19, and PM200 is the 50%wt of adhesive gross weight, and water-soluble polyester is the 10%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

The 70g of adhesive 19 is joined (PM200 and water-soluble polyester be 42g altogether, and PM200 accounts for the 3.5%wt of wood shavings amount) in the 1000g wood shavings.The particieboard performance of producing is seen table 2.

Embodiment 20:

The method dissolving water-soluble polyester 6 of reference implementation example 1 obtains polyester aqueous solution 20A (water-soluble poly ester content 35%wt).The water-soluble fluid power of this polyester is deposited and was not changed in 30 days.

With reference to embodiment 8: in having the container of stirring, adding PM200 is 100g, and the water-soluble poly aqueous solution of ester 20A of 35%wt is 100g, and stirring obtains adhesive 20.PM200 is that 100 weight portions are counted 100 parts with the water-soluble poly aqueous solution of ester in the said adhesive 20, and PM200 is the 50%wt of adhesive gross weight, and water-soluble polyester is the 17.5%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

The 70g of adhesive 19 is joined (PM200 and water-soluble polyester be 47.2g altogether, and PM200 accounts for the 3.5%wt of wood shavings amount) in the 1000g wood shavings.The particieboard performance of producing is seen table 2.

Embodiment 21:

With reference to embodiment 8: in having the container of stirring, adding PM200 is 60g, and the water-soluble poly aqueous solution of ester 1A of 30%wt is 140g, and stirring obtains adhesive 21.PM200 is that 100 weight portions are counted 43 parts with the water-soluble poly aqueous solution of ester in the said adhesive 21, and PM200 is the 30%wt of adhesive gross weight, and water-soluble polyester is the 21%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

The 120g of adhesive 21 is joined (PM200 and water-soluble polyester be 61.2g altogether, and PM200 accounts for the 3.6%wt of wood shavings amount) in the 1000g wood shavings.The particieboard performance of producing is seen table 2.

Embodiment 22:

With reference to embodiment 8: in having the container of stirring, adding PM200 is 110g, and the water-soluble poly aqueous solution of ester 1A of 30%wt is 90g, and stirring obtains adhesive 22.PM200 is that 100 weight portions are counted 122 parts with the water-soluble poly aqueous solution of ester in the said adhesive 22, and PM200 is the 55%wt of adhesive gross weight, and water-soluble polyester is the 13.5%wt of adhesive gross weight.This adhesive room temperature is placed no significant change in 4 hours.

The 70g of adhesive 21 is joined (PM200 and water-soluble polyester be 48g altogether, and PM200 accounts for the 3.85%wt of wood shavings amount) in the 1000g wood shavings.The particieboard performance of producing is seen table 2.

Embodiment 23:

With reference to embodiment 8: different is joins (PM200 and water-soluble polyester be 32.5g altogether, and PM200 accounts for the 2.5%wt of wood shavings amount) in the 1000g wood shavings with the 50g of adhesive 1, and the particieboard performance is seen table 2.

Comparative example 11:

With reference to embodiment 8, different is the water-soluble poly ester solution with 5%wt, obtains contrasting adhesive 11.PM200 content is 50%wt in the contrast adhesive 11, and the water-soluble poly ester content is 2.5%wt.This adhesive 80g is joined 1000g prepare environmental protection particieboard (PM200 and water-soluble polyester be 42g altogether, and PM200 accounts for the 4.0%wt of wood shavings amount).The particieboard performance is seen table 2.

Comparative example 12:

With reference to embodiment 8, different is joins (PM200 and water-soluble polyester be 19.5g altogether, and PM200 accounts for the 1.5%wt of wood shavings amount) in the 1000g wood shavings with the 30g of adhesive 1.The particieboard performance is seen table 2.

Comparative example 13:

In having the container of stirring, adding polyisocyanates PM200 is 130g, and the water-soluble poly aqueous solution of ester 1A of 30%wt is 70g, stir contrast adhesive 13.PM200 content is 65%wt in the contrast adhesive 13, and the water-soluble poly ester content is 10.5%wt.PM200 is that 100 parts by weight are counted 186 parts with adhesive.This adhesive room temperature is placed no significant change in 4 hours.

Press embodiment 5 particieboard production technologies, the 52g that contrasts adhesive 13 is joined (PM200 and water-soluble polyester be 39g altogether, and PM200 accounts for the 3.38%wt of wood shavings amount) in the 1000g wood shavings.With reference to the prepared environmental protection particieboard of embodiment 1, the particieboard performance is seen table 2.

Comparative example 14:

In having the container of stirring, adding PM200 is 30g, and the water-soluble poly aqueous solution of ester 1A of 30%wt is 170g, stir contrast adhesive 14.PM200 content is 15%wt in the contrast adhesive 14, and the content of water-soluble polyester is 25.5%wt.PM200 is that 100 parts by weight are counted 18 parts with adhesive.This adhesive room temperature is placed no significant change in 4 hours.

Press embodiment 5 particieboard production technologies; The 200g of contrast adhesive 14 is joined (PM200 and water-soluble polyester be 81g altogether, and PM200 accounts for the 3.0%wt of wood shavings amount) in the 1000g wood shavings, with reference to the prepared environmental protection particieboard of embodiment 1; Because moisture is excessive, the particieboard layering.

Table 2

Claims (13)

1. environment friendly artificial board, its raw material packet contains following component: adhesive and wood-based plate bits material; Wherein said adhesive comprises the aqueous solution of isocyanates and water-soluble polyester; The content of isocyanates is 100 parts by weight in the aqueous solution of water-soluble polyester, is 25～150 parts, is preferably 40～125 parts; The content of water-soluble polyester is 10～40%wt in the aqueous solution of water-soluble polyester, is preferably 20～35%wt; Said water-soluble polyester adopts dicarboxylic acids, dihydroxylic alcohols and hydrophilic monomer to form for the base stock copolymerization, and said hydrophilic monomer is selected from M-phthalic acid-5-sulfonate or derivatives thereof, and content is 5～20%mol of dicarboxylic acids molal quantity in the water-soluble polyester; The degree of functionality that said water-soluble polyester contains branching is greater than 2 polyol component, and content is 0.3～3.0%mol of dicarboxylic acids molal quantity in the water-soluble polyester; The inherent viscosity of said water-soluble polyester is 0.25～0.50dL/g; Isocyanates weight accounts for 2.0～8%wt of wood-based plate bits material dry weight in the wherein said adhesive.

2. environment friendly artificial board according to claim 1 is characterized in that:

Isocyanates weight accounts for 2.5～6.0%wt of wood-based plate bits material dry weight in the said adhesive.

3. environment friendly artificial board according to claim 1 is characterized in that:

Isocyanates is a degree of functionality greater than 2 polyisocyanates in the said adhesive.

4. environment friendly artificial board according to claim 1 is characterized in that:

Isocyanates is selected from least a in the following material in the said adhesive: toluene di-isocyanate(TDI), diphenyl methane-4; 4 '-vulcabond, 1; Hexamethylene-diisocyanate, XDI, naphthalene-vulcabond, poly methylene poly phenyl poly isocyanate, polymeric isocyanate, triphenylmethane triisocyanate.

5. environment friendly artificial board according to claim 1 is characterized in that:

Polyalcohol in the said adhesive in the water-soluble polyester is selected from least a in trihydroxylic alcohol, the tetrahydroxylic alcohol, preferably at least a in glycerine, orthoformic acid, pentaerythrite.

6. environment friendly artificial board according to claim 1 is characterized in that:

The degree of functionality of the branching that the water-soluble polyester in the said adhesive contains is greater than 2 polyalcohol, and its content is 0.5～2.0%mol of dicarboxylic acids molal quantity in the water-soluble polyester.

7. environment friendly artificial board according to claim 1 is characterized in that:

Said hydrophilic monomer is selected from least a in the following material: 5-sodium sulfo isophthalate, M-phthalic acid-5-sulfonic acid lithium, 5-sodium sulfo isophthalate glycol ester.

8. water environment friendly artificial board according to claim 1 is characterized in that:

Its content of the hydrophilic monomer that contains in the said water-soluble polyester is 8～16%mol of dicarboxylic acids molal quantity in the water-soluble polyester.

9. environment friendly artificial board according to claim 1 is characterized in that:

The dicarboxylic acids of said water-soluble polyester is selected from least a in terephthalic acid (TPA), adipic acid, decanedioic acid, the M-phthalic acid etc.; Dihydroxylic alcohols is selected from least a in ethylene glycol, propane diols, the butanediol.

10. environment friendly artificial board according to claim 9 is characterized in that:

The content of terephthalic acid (TPA) accounts for the 70mol% of total amount at least in the dicarboxylic acids of said water-soluble polyester, preferably accounts for the 80mol% of total amount at least; Glycol content accounts for the 60mol% of total amount at least in the dihydroxylic alcohols, preferably accounts for the 70mol% of total amount at least.

11. preparation method according to each described environment friendly artificial board of claim 1～10; It is characterized in that: said adhesive and wood-based plate bits material is mixed by said amount, mat formation through comprising, the step of precompressed, hot pressing, side cut makes environment friendly artificial board.

12. the preparation method of environment friendly artificial board according to claim 11 is characterized in that:

Said adhesive is made by the preparation method who may further comprise the steps:

(1) earlier said water-soluble polyester is dissolved in the aqueous solution of processing water-soluble polyester in the water by said amount;

(2 with the aqueous solution of above-mentioned water-soluble polyester with include said isocyanates and mix by said amount in interior component, obtain said adhesive after stirring.

13. the preparation method of environment friendly artificial board according to claim 11 is characterized in that:

Said adhesive prepares the back and is less than 4 hours to mix the preceding resting period with wood-based plate bits material.