CN109927146A - A kind of isocyanate adhesive system and the method for wood-based plate and the wood-based plate of preparation are prepared with it - Google Patents
A kind of isocyanate adhesive system and the method for wood-based plate and the wood-based plate of preparation are prepared with it Download PDFInfo
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Abstract
The present invention discloses a kind of isocyanate adhesive system and prepares the method for wood-based plate and the wood-based plate of preparation with it.Described adhesive system, comprising: (a) polyfunctionality isocyanates and acid compound；(b) polyalcohol, amines catalyst and optional iron containing compounds；With optional (c) water-based emulsion.Described method includes following steps: component (a) being applied to whole substrates, component (b) is applied to sandwich layer, component (c) is applied to surface layer；Then substrate is mated formation, the techniques such as hot pressing, obtains the wood-based plate.It can be obviously improved hot pressing efficiency, reduce precuring degree of the adhesive in wood shavings after sizing, improve adhesive utilization rate；The problem of tack that particieboard cold pressing slab can be improved solves in current PMDI particieboard production, and slab tack is poor, can not be by conveyer belt transition gap.Described adhesive system especially suitable for particieboard (PB) and can facing oriented wood chipboard (OSB) production.
Description
Technical field
The present invention relates to a kind of isocyanate adhesive system, it is specifically related to be used to prepare the adhesive composition of wood-based plate
And its method for being used to prepare wood-based plate.
Background technique
It is machined to be separated into particle, needle-shaped or sheet wood shavings, fiber using timber or other Non-woody plants as raw material
After equal units, applies adhesive or other additives through hot pressing into wood-based plate, develop in recent years very rapidly.Conventional artificial's plate
Product mainly includes glued board, particieboard, the big plate kind of fiberboard three, and extension product or deep processed product reach hundreds of.People
The birth for making plate, is the beginning of timber reprocessing modernization, has extended to change wood performance from log shapes are changed, has been modern
The product of industrial progress.Wood-based plate can be improved the utilization rate of timber, save the forest reserves, and 1 cubic metre of wood-based plate can replace 3~
5 cubic metres of logs use.
Traditional urea formaldehyde resin adhesive, aerodux and melamine urea-formaldehyde resin adhesive are in use
And can be generated by formaldehyde in finished product plate, environment is polluted, human health is endangered.
Novel PMDI (polymethylene multi-phenenyl isocyanate) adhesive can solve Form aldehyde release problem, due to PMDI sheet
Body does not contain formaldehyde components, environmentally protective without artificial addition Form aldehyde release in manufactured plate；The standby plate of hot pressing simultaneously
There is plate compared with urea-formaldehyde glue preparation preferable water resistance to be still able to satisfy national standard to suction in the case where not adding waterproofing agent
The requirement (2h, 20 DEG C of water-bath expansion rate of water absorption≤8%) of water expansion rate.
PMDI prepares wood-based plate, reaction mechanism big portion under hot-pressing high-temperature for the functional group-NCO in PMDI as adhesive
Divide and reacted with the water in timber or non-wooden plant material, produces urea (- NH-CO-NH-) and biuret (- NH-CO-N-CO-
The products such as NH-) generate cementation with material unit, form the artificial board for meeting national standard, and entire reaction process is without having
Evil substance generates.Because reaction mechanism is different from urea formaldehyde resin adhesive, therefore uses PMDI as wood adhesive reaction member
Higher water content can be retained, this can save the cost of factory's timber drying to a certain extent.
Hot pressing board making process is related to complicated energy variation, includes heat and mass transfer process.Surface layer is preferentially heated, in unit
Moisture is heated to become water vapour, carries heat and transmits to sandwich layer.With the extension of time, core layer temperature rises, reach adhesive
Solidification temperature after, under the effect of the pressure, curing molding.Since wood materials are the non-conductor of heat, master in hot pressing
The heat transfer wanted is steam carrying.Restricting hot pressing efficiency principal element is that sandwich layer heating is slow, and PMDI adhesive reacts speed with water
Rate is slow.It improves productivity most directly to show as shortening hot pressing time, but sandwich layer adhesive can still solidify well interior combination
Intensity will not be substantially reduced；It keeps hot pressing time constant, the internal bond strength of plate can be made to significantly improve, also be understood as being promoted
The solidification rate of sandwich layer adhesive.
PMDI is manufactured as a new direction of aldehyde-free artificial board development in recent years, more and more enterprises for wood-based plate
Start the production of progress aldehyde-free artificial board.But it compared to (200-230 DEG C) under conditions of traditional urea-formaldehyde glue hot pressing temperature, uses
PMDI adhesive carries out hot pressing and will be greatly reduced production efficiency for particieboard (PB) or oriented wood chipboard (OSB), and then subtracts
Few production capacity；And since PMDI glue itself is without tack, the slab adhesive after precompressed is poor, is difficult to pass through hot press in continuous lines
Transition belt causes slab to collapse, and influences the efficiency of plating, this is that enterprise is undesirable.
Wood-based plate structural unit is living by links, isocyanate groups such as conveyer belt transport, feed bin storages after sizing
Property it is big, higher workshop temperature can make some adhesive solidify (precuring), cause plate property insufficient；Settling mode is generally adopted
With adhesive additive amount is increased, lead to that the production cost increases.
A kind of wood-based plate isocyanate adhesive system is needed to solve the above technical problem.
Summary of the invention
It is an object of the invention to overcome isocyanates as adhesive production wood-based plate low efficiency, slab adhesive difference
Disadvantage provides a kind of isocyanate adhesive system that wood-based plate hot pressing efficiency and slab adhesive can be improved and prepares artificial
The method of plate improves wood-based plate hot pressing efficiency under the premise of not changing original plant production processes；Plane can also be extended simultaneously
Flower assembly time, reduces adhesive precuring degree；Slab adhesive is improved, heat is passed through with intact form after guarantee slab precompressed
Press conveyer belt transition region, makes finished product plate without mark of break.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of for producing the isocyanate adhesive system of wood-based plate, including following components:
(a) polyfunctionality isocyanates and acid compound；
(b) polyalcohol, amines catalyst and optional iron containing compounds；With
Optional (c) water-based emulsion.
Polyfunctionality isocyanates of the present invention includes many kinds, be can choose one of or several as main
Raw material.Isocyanates refers to the compound for containing isocyanates (- NCO) group in structure, can be used as adhesive use.Polyisocyanic acid
The design feature that ester can be connect according to isocyanate group with carbon atom is divided into four major class: aromatic polyisocyanate (such as toluene
Diisocyanate, i.e. TDI), aliphatic polyisocyante (hexamethylene diisocyanate, i.e. HDI), araliphatic polyisocyanic acid
Ester (aliphatic group is embedded with i.e. between aryl and multiple isocyanate group --- it is often polymethylene, as phenylenedimethylidyne two is different
Cyanate, i.e. XDI) and alicyclic polyisocyanates (i.e. on cycloalkane have multiple isocyanate group, as isophorone two is different
Cyanate, i.e. IPDI) four major class.Polyfunctionality isocyanates using any kind in above-mentioned four major class or a combination thereof exists
Within present disclosure.The aromatic isocyanates of relative low price is different as preferred raw materials, including toluene two
Cyanate (TDI), methyl diphenylene diisocyanate (MDI) and polymeric diphenylmethane diisocyanate (polymeric MDI or
PMDI).The adhesive for being widely used in industry of artificial boards production PB and OSB is polymeric MDI, and scientific name is polymethylene polyphenyl
Isocyanates, structural formula are as follows:
PMDI is a kind of mixture of the polyisocyanates of different degrees of functionality, wherein the diisocyanate (i.e. MDI) of n=0
40% or so, the MDI structure of mixture is accounted for based on 4,4 '-MDI, 2,4 '-a small amount of MDI isomers may be contained.With adjustment
Content of isomer is raw material, and the isocyanates that satisfaction-NCO mass fraction is 30-34% is also within announcement.Remaining in PMDI
Ingredient be 3~5 degree of functionality low polymerization degree polyisocyanates, PMDI average molecular weight is 320-420, and average functionality is
2.5-3.0, viscosity is about 150-250cP at 25 DEG C.
But use any other modified product based on PMDI or TDI or MDI or combinations thereof product for raw material, packet
Polyethers, polyester modification are included but are not limited to, gained-NCO mass fraction is 20-34%, and viscosity is less than 10000cP at 25 DEG C,
Belong in the polyfunctionality isocyanates raw material that the present invention announces.As the main component of adhesive composition, preferably degree of functionality is
2.6-2.8, the polymethylene multi-phenenyl isocyanate (PMDI) of viscosity 150-250cP at 25 DEG C.
Polyalcohol in component (b) of the present invention, including polyether-type, polyester-type two major classes are in polyurethane chemistry
The soft segment of polyurethane is constituted, hydrophily is preferable, can improve the hydrophily of isocyanates after reacting with-NCO.
Polyester polyol be usually by Dicarboxylic Acids (acid anhydrides or ester) and polyalcohol (including glycol) condensation (or ester hand over
Change) or formed by lactone and polymerization, ester bond (- COO) and terminal hydroxy group (- OH) are contained in strand.Polyether polyol letter
Claim polyethers, is also poly- alkane ether or polyoxygenated alkene, is in the presence of active hydrogen compounds are as initiator and catalyst by ring
Oxygen compound ring-opening polymerisation is made.Common epoxide has ethylene oxide, propylene oxide, tetrahydrofuran etc..By a kind of ring
The polyethers of oxygen compound monomer synthesis is equal polyethers, and the polyethers synthesized by two or more epoxide is copolymerization
Object.According to the difference of charging sequence and proportion, random copolymerization polyethers and orderly distribution or the block copolymerization of disorder distribution are produced
Ether.Or mixtures thereof the polyethers for the terminal hydroxy group that can choose in the scheme or polyester polyol, preferred, polyethers polyalcohol.In the presence of
Polyether polyol in specific embodiment, mainly contains primary hydroxyl, may contain micro secondary hydroxyl.
The polyether polyol used in the present invention, including it is polyethylene oxide polyol, polyoxypropylene polyol, poly-
One of ethylene oxide and polyoxypropylene polyol mixture and its copolymer or multiple combinations；It is preferred that there is ethylene oxide
Ethylene oxide polyol made of ring-opening polymerisation.Obtain polyether polyol in addition to needing epoxy monomer, also need catalyst (KOH) and
Initiator (polyalcohol or amine) is to control rate of polymerization, molecular weight and its degree of functionality.Polymerization reaction formula can be indicated with general formula are as follows:
Wherein YHnFor initiator, there are commonly polyalcohol (or amine), n is degree of functionality, and x is the degree of polymerization, and R is hydrogen or alkane
Base.From the above equation, we can see that the degree of functionality of polyether polyol is equal with the degree of functionality of initiator；And a starter molecules generate one
A polyether polyol macromolecular；The method of adjusting initiator dosage and degree of functionality be can use to control the molecule of polyether polyol
Amount and degree of functionality.
Polyethylene oxide polyol according to the present invention, by adjusting the x degree of polymerization, polyether polyol molecular weight is 200-
8000, preferred molecular weight 800-5000.
About polyether polyols alcohol functionalities, a variety of alcohol and amine substance can be used as initiator carry out official in the present invention
Energy degree is adjusted.Initiator includes but is not limited to listed substance, such as propylene glycol, butanediol, glycerol, trimethylolpropane, second two
Amine, pentaerythrite, xylitol, diethylenetriamines, sorbierite, bisphenol-A, bisphenol S, toluenediamine etc..And these substances
Combination.It is the hydroaropic substance of 2-6 as initiator, the glycerol or three of more preferable 3 degree of functionality that degree of functionality, which can be used, in the present invention
Hydroxymethyl-propane or both mixture is as initiator, and polyalcohol and the polyfunctionality in component (a) are different in the component (b)
Cyanate weight ratio is 0.01-0.2:1, preferably 0.06-0.12:1.
The present invention improves the speed that hot pressing isocyanate adhesive is reacted with water by adding a small amount of aminated compounds
Rate.For polyurethane chemistry, catalyst can substantially be divided into two classes, and one kind is tertiary amine catalyst, and one kind is gold
Belong to alkyl compound.Isocyanate adhesive system in the present invention selects a small amount of trimethylamine as catalyst, improves different
The rate that cyanate is reacted with water.Tertiary amine (R3It N) is ammonia (NH3) the product that is replaced by alkyl (R) of 3 hydrogen atoms, comprehensive alkane
The effect of the three-dimensional effect and inductive effect of base, the alkaline size order of amine are as follows: secondary amine > primary amine > tertiary amine, so the alkalinity of tertiary amine
It is very weak.But the catalytic action of tertiary amine is not only related with its alkalinity, it is often more important that by the sky of substituent group on tertiary N atom
Between effects.Tertiary amine catalyst has preferable catalytic action to the isocyanate adhesive in the present invention, can be catalyzed its with
Water fast reaction.The selectable tertiary amine catalyst of the present invention include but is not limited to it is following several, such as triethylenediamine, three second
Amine, N, N- dimethyl cyclohexyl amine, N, N- methyl bicyclic base amine, N-methylmorpholine, N-ethylmorpholine, N, N '-dimethyl piperazine
Piperazine, N, N '-diethyl piperazine, 1,1,3,3- tetramethyl piperidine, bis- (2- dimethylaminoethyl) ethers, tetramethyl butane diamine, 2,4,
6- tri- (dimethylamino methyl) phenol etc..Amines catalyst of the present invention can choose but be not limited to above-mentioned listed catalyst
One or more combination, additive amount can be according to the 100- of the polyfunctionality isocyanate weight in the component (a)
10000ppm addition, preferably 1000-3000ppm.
A kind of acid compound additive is further related in isocyanate adhesive system of the invention, can select gas
HCl is acidified isocyanates, and acyl chlorides can also be added in isocyanates.Acyl chlorides refers to containing-C (O) Cl functional group
Compound belongs to one kind of carboxylic acid halides, is the carboxylic acid derivates formed after hydroxyl in carboxylic acid is replaced by chlorine.Described adhesive system
It is added in wood-based plate structural unit, its reactivity is also larger at room temperature, does not enter in raw material and just has portion in hot press
Divide reaction, adhesive is caused to waste.By adding acid compound, it is suitable for reduction-NCO group activity, reduces isocyanic acid
The precuring of ester adhesive improves the resting period of material unit.The selected acyl chlorides of the present invention includes but is not limited to listed
Following several, such as trimethyl-aceyl chloride, paraphthaloyl chloride, Adipoyl Chloride, isobutyryl chloride, positive caprylyl chloride.Present invention choosing
Use one of perhaps several acyl chlorides as additive or directly using gas HCl to the polyfunctionality isocyanide in component (a)
Acid esters carries out acidification, and the acid value of the component (a) is calculated as 200-10000ppm, preferably 500- with HCl after addition
3000ppm。
Isocyanate adhesive system of the invention it is optional use iron containing compounds as additive, make an addition to component
(b) in.Iron containing compounds include any organic or inorganic compound containing iron, can choose ferrous salt, molysite is added,
Include but are not limited to substance set forth below, such as FeCl2、FeSO4、FeCl3、 Fe2(SO4)3、Fe(NO3)3, ferric acetyl acetonade,
Ferrous lactate, ironic citrate etc., present invention preferably uses one of or several inorganic molysite that contain as additive, more preferably
FeCl3And/or Fe2(SO4)3As additive, additive amount, can be according to polyfunctionality isocyanates in the component (a) in terms of iron
The 20-2000ppm of weight is added, preferably 200-1000ppm.
Component (c) water-based emulsion can also be contained in isocyanate adhesive system of the invention, included but are not limited to
PVA (polyvinyl alcohol) lotion, EVA (vinyl-vinyl acetate copolymer) lotion, PVAc (polyvinyl acetate) lotion, propylene
Yogurt liquid, PUD (aqueous polyurethane) lotion and its mixture.Selected water-based emulsion all has certain viscosity, with cream
The volatilization of liquid moisture generates bond effect under the action of poly- power in the molecule.
PVA be white plates, cotton-shaped or pulverulent solids, physical property by chemical structure, alcoholysis degree, the degree of polymerization shadow
It rings.There is two kinds of chemical structures, i.e. 1,3- and 1,2- ethylene glycol structures in polyvinyl alcohol molecule, but main structure is 1,
3- ethylene glycol structure, i.e. structure " end to end ".The degree of polymerization of polyvinyl alcohol is divided into the superelevation degree of polymerization (molecular weight 25~300,000), Gao Ju
Right (molecular weight 17-22 ten thousand), the middle degree of polymerization (molecular weight 12~150,000) and low polymerization degree (2.5~3.5 ten thousand).Alcoholysis degree one
As have 78%, 88%, 98% 3 kind.The alcoholysis degree of partial alcoholysis is usually 87%~89%, and the alcoholysis degree of complete alcoholysis is
98%~100%.The dissolubility of polyvinyl alcohol has very big difference with the height of its alcoholysis degree: the product of alcoholysis degree 87%~89%
It is water-soluble best, regardless of still can soon be dissolved in the hot water in cold water and show maximum solubility；Alcoholysis degree
In 90% or more product, in order to be completely dissolved, it need to generally be heated to 60~70 DEG C；The polyethylene that alcoholysis degree is 99% or more
Alcohol is dissolved only in 95 DEG C of hot water；And alcoholysis degree is dissolved only in cold water in 75%~80% product, does not dissolve in hot water；Alcoholysis degree is less than
66%, since the acetyl content of hydrophobic increases, water solubility decline；Until alcoholysis degree 50% is hereinafter, polyvinyl alcohol is no longer molten
Xie Yushui.
EVA lotion is total to other auxiliary materials by emulsion polymerisation process using vinyl acetate and vinyl monomer as base stock
Macromolecule emulsion made of poly- has preferable toughness and resistance to acid and alkali as PVAc lotion, is that a kind of common timber is viscous
Mixture.Preparation method about EVA lotion can refer to Chinese patent CN106753069A " a kind of vinyl acetate adhesive and its
Preparation method " Ji Chenzhao rock et al. document " EVA lotion production technology and market analysis ".Preparation method about PVAc lotion
It can refer to Chinese patent CN101010347 " poly- (vinyl acetate) lotion and preparation method thereof " and Cui Huiwang et al. document
" PVAc preparation method and technique ".
Acrylic emulsion is also a kind of common decoration film forming agent, is had a certain degree of cohesiveness, preparating mechanism: vinyl list
Body carries out emulsion polymerization under the action of initiator and emulsifier.Initial reaction stage forms monomer dispersion liquid in water, each monomer
Dispersant liquid drop is exactly the place of a bulk polymerization, wherein the reaction such as the initiation of chain, the growth of chain and end stopping of chain occurs.
With the progress of reaction, dispersion liquid can gradually form latex to monomer in water.Specific preparation method can refer to Chinese patent
CN106397659A " a kind of high-performance polypropylene yogurt glue and preparation method thereof " and CN107163181A " acrylic emulsion and its
Preparation method ".
PUD refer to polyurethane be dissolved in water or be dispersed in water and the adhesive that is formed, also referred to as aqueous polyurethane or water base
Polyurethane.According to its appearance and partial size, aqueous polyurethane is divided into three classes: (partial size < 0.001um, appearance are saturating for aqueous polyurethane
It is bright), polyurethane dispersing liquid (partial size 0.001-0.1um, translucent appearance), polyaminoester emulsion (partial size > 0.1um, appearance gonorrhoea).
But two classes are referred to as polyaminoester emulsion or polyurethane dispersing liquid again after traditionally.Aqueous polyurethane is according to the charge of hydrophilic radical
Matter can be divided into anion-type water-thinned polyurethane, cation-type water-thinned polyurethane and non-ion aqueous polyurethane.Wherein anion
Type is mostly important, is divided into carboxylic acid type and sulfonic acid type two major classes.Polyether-type, polyester can be divided into according to synthon difference aqueous polyurethane
Type and polyethers, polyester mixed type.According to the difference of the diisocyanate of selection, aqueous polyurethane can be divided into aromatic series and fat again
Race, or be specifically divided into TDI type, HDI type etc..The entire synthesis process of aqueous polyurethane can be divided into two stages.First stage is pre-
Gradually it polymerize, i.e., gradually polymerize opposite point of generation by solution by oligomer diol, chain extender, aqueous monomers, diisocyanate
Protonatomic mass is the Waterborne Polyurethane Prepolymer of l000 magnitude；Second stage is the dispersion of performed polymer in water after neutralizing.
The present invention can choose a kind of above-mentioned water-based emulsion or the mixing of several water-based emulsions is carried out using dosage can basis
Wood shavings actual conditions account for, the weight of polyfunctionality isocyanates in the dosage (with solid part) and component (a) of water-based emulsion
Amount is than being 0.05-1:1, preferably 0.1-0.5:1.
In addition to the main component of the isocyanate adhesive system, other class additives known to polyurethane chemistry, packet
Fire retardant, solvent, release agent, colorant, filler, mould inhibitor, antistatic agent, antioxidant and light stabilizer, plasticizer etc. are included,
It is contained in other compounding agents of the invention.The application method of these additives is selectable as independent material stream and is added
Add, is added it is furthermore preferred that being incorporated in (b) described above and/or (c) two strands of material streams.
The present invention also provides a kind of preparation method of artificial board, include the following steps:
(1) a kind of wooden or non-wood particle comprising meeting production requirement, wood shavings are provided as substrate；
The substrate includes plurality of raw materials component, can be the crushing such as conventional wood, including poplar, pine, Eucalyptus generation
Wood substance grain and wood shavings, be also possible to the non-wood unit such as wheat, rice, bagasse, cotton stem, reed be process it is wooden
Particle.In a preferred approach, selected substrate is ligno-cellulosic materials, most preferably production particieboard or oriented shaving board raw material
Substrate；
(2) a kind of isocyanate adhesive system of the present invention is provided, described adhesive system includes polyfunctionality
Isocyanates, acid compound, polyalcohol, amines catalyst, optional iron containing compounds and optional water-based emulsion.It is wherein described
Adhesive composition is formulated into multiple independent material streams, in which: a material stream includes (a) polyfunctionality isocyanates and acid
Property compound；Second material stream includes (b) polyalcohol, amines catalyst and optional iron containing compounds；If using (c) aqueous
Lotion, then third material stream includes (c) water-based emulsion；
(3) the multiple independent material stream is uniformly added to base without premix in the form of meeting resin application methods
In material；
In the method preferred embodiment, the multiple independent material stream is applied to artificial board substrate
In.The combination that rotary-atomizing or high-pressure atomization or both can be used in each independent material stream is added；Add place choosing
It selects in the closed roller that can complete to be stirred, mixes corresponding material stream with artificial board substrate's unit more uniform.
It is furthermore preferred that first material stream is applied to whole substrates, second material stream is applied to sandwich layer, can be according to second material
It is added after the ratio mixing that the weight ratio of stream and water is 1:1 to 1:5, improves dispersing uniformity；If using third material stream,
Then third material stream is preferably applied to surface layer, the ratio that can be 1:1 to 1:5 according to the weight ratio of third material stream and water
It is added after mixing, improves dispersing uniformity；
(4) by gained substrate in step (3) by mating formation, the technical process such as hot pressing obtain the wood-based plate.
Preferably, the artificial board substrate's unit for adding adhesive composition is carried out being layered making sheet of mating formation.Laboratory
Substrate material is mated formation on the metal caul by release agent processing when operation, and is limited with the box mold of limitation size
System, prevents extra material to be scattered at edge.After adhesive application, lower temperature should be maintained to carry out link of mating formation as far as possible.?
Before compacting, substrate and adhesive composition come into full contact with and expose in air, and the time is longer, the degree of isocyanates precuring
Bigger, the adhesive for directly resulting in effectively bonding substrate reduces, and sheet forming mechanical property reduces.Due to carrying out sheet-making operation
Each process require the regular hour, preferred hot pressing carries out within 2 hours after sizing, more preferably 1 hour it
Interior progress, further preferably carries out within 0.5 hour.The acid compound additive can suitably reduce the pre- of adhesive
Curing degree, the wood shavings substrate after sizing were displayed in 0.5 hour, and sheet mechanical property does not significantly reduce.
In the industrial production, mated formation using spreading head or roller of mating formation to substrate unit, before entering hot press, needed
Precompressed is carried out to slab, make plate construction relative close, certain thickness is maintained to enter hot press, the addition energy of water-based emulsion
Make slab that complete form be maintained to enter hot press to be scattered without collapsing.Hot pressing time is more long, the mechanical property of sheet forming
Can be better, this is because adhesive has obtained sufficient solidification；But hot pressing time causes production efficiency to reduce long, this is enterprise
It is undesirable.Using adhesive composition of the present invention, hot pressing time can be reduced suitably to improve production efficiency, production effect
Rate can promote 15% or more, bring sizable benefit to factory.
Edge flash is carried out after slab hot pressing to cut, and according to requirement, is cut into fixed dimension and is carried out displaying processing, then
Certain sanding, the subsequent processings such as veneer obtain final product.
Adhesive composition of the present invention includes polyfunctionality isocyanates, polyalcohol, amines catalyst, acid chemical combination
Object, optional iron containing compounds and water-based emulsion, it is possible to reduce the precuring of adhesive at room temperature, reaching reduces cost, improves life
Produce the purpose of efficiency；The adhesive after slab precompressed is improved simultaneously, guarantees to be scattered in production process of plate without collapsing, finished product plate
Without mark of break.
Detailed description of the invention
Fig. 1,2,3 are respectively slab transition screenshot after embodiment 12, the cold pressing of 13 comparative examples 5.
Specific embodiment:
Embodiment of the present invention is further illustrated below with reference to embodiment, but the present invention is not limited to listed implementations
Example should also include other any well known changes in interest field of the presently claimed invention.
Polymethylene multi-phenenyl isocyanate (PMDI): degree of functionality about 2.7, viscosity is 180-250cP at 25 DEG C ,-
NCO content 30.5-32%, Wanhua Chemical Group Co., Ltd.；
Polyether polyol: polyethylene oxide polyol, number-average molecular weight 800 are caused by glycerol, degree of functionality 3, Wan Hua
Rong Wei；Polyethylene oxide polyol, number-average molecular weight 5000, is caused by glycerol, degree of functionality 3, Wan Huarong prestige；
Water-based emulsion: acrylic emulsion, Archsol 8016, solid content 52%, Wanhua Chemical Group Co., Ltd.；
EVA lotion, DA102, solid content 55%, Dalian chemical industry (Jiangsu) Co., Ltd；
Release agent, PAT-7399/C, German Huo Shi company；
Wood raw material, table core layer raw material used for shaving board, water content about 3wt%, poplar, self-control.
Embodiment 1:
Component (a) selects PMDI, adds paraphthaloyl chloride, PMDI acid value (in terms of HCl) is adjusted to 500ppm；Component
(b) it is the polyether polyol of number-average molecular weight 800, adds triethylenediamine, additive amount 1000ppm, FeCl3(in terms of Fe)
Additive amount is 200ppm (PMDI is 1 mass parts)；Resin added is wood shavings dry ratio.
Particieboard preparation step:
By in the sealing drum of the wood shavings lead-in zone mixing plant of certain mass, material is carried out in the way of high-pressure atomization and is added
Add.Component (a) adding rate is controlled in 1g/s, and component (b) is diluted using the water of 5 times of quality, and adding rate is controlled in 1g/
S, it is ensured that adhesive component can be uniformly applied in wood shavings.Addition manner is that component (a) is added to watch core layer wood shavings, component
(b) only it is added in sandwich layer wood shavings.Surface layer wood shavings water content is 11.75wt%, and sandwich layer wood shavings water content is 8.59wt%.
Release agent is sprayed after 50*50cm stainless steel metal backing plate is put into hot press preheating, by the way of mating formation by hand
It carries out particieboard in the box mold of 35*35cm to mat formation, watch core layer ratio of mating formation is carried out according to 1:3:1.It is carried out after mating formation
Hot pressing, finger gauge 18mm.Hot pressing uses 3 segmentation pressure, is divided into high, normal, basic three sections, dwell time ratio is 4:4:3, hot pressing
The factor is 6s/mm, and hot pressing temperature is 220 DEG C.
It carries out displaying for 2-3 hours at room temperature after hot pressing, panel density be tested after cutting, according to national standard " GBT
17657-2013 test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels " carry out internal bond strength (IB), surface bonding strength
(SB), elasticity modulus (MOE), quiet bent modulus (MOR), expansion rate of water absorption (2h-TS) test in 2 hours.
Making sheet design parameter is shown in Table 1, and plate property is shown in Table 2.
Embodiment 2~6
Embodiment 2 or 6 raw material types and embodiment 1 are identical；It is 5000 that embodiment 3, which selects polyether polyol molecular weight,
Remaining raw material type is same as Example 1；The molysite of component (b) selects Fe in embodiment 42(SO4)3, dosage is calculated as with Fe
1000ppm (PMDI is 1 mass parts), remaining raw material type is same as Example 1；The amines catalyst of component (b) in embodiment 5
Selection tetramethyl butane diamine, additive amount 3000ppm, remaining raw material type are same as Example 1.Design parameter is shown in Table 1, plate
Performance is shown in Table 2.
Comparative example 1~2
1 center core layer of comparative example not addO-on therapy (b)；Molysite is not added in 2 component (b) of comparative example, corresponding making sheet is specifically joined
Number is shown in Table 1, and, referring to embodiment 1, plate property is shown in Table 2 for remaining.
1 plate design parameter of table
2 plate property of table
| IB/Mpa | SB/Mpa | MOE/Mpa | MOR/Mpa | 2h-TS | |
| Embodiment 1 | 0.57 | 0.92 | 2616 | 16.38 | 3.83% |
| Embodiment 2 | 0.60 | 0.94 | 2754 | 16.95 | 3.94% |
| Embodiment 3 | 0.56 | 0.91 | 2742 | 16.35 | 3.77% |
| Embodiment 4 | 0.61 | 0.89 | 2712 | 16.23 | 3.89% |
| Embodiment 5 | 0.62 | 0.93 | 2679 | 16.42 | 4.11% |
| Embodiment 6 | 0.44 | 0.90 | 2456 | 16.11 | 4.03% |
| Comparative example 1 | 0.45 | 0.95 | 2535 | 16.21 | 3.52% |
| Comparative example 2 | 0.53 | 0.91 | 2589 | 16.25 | 3.88% |
As shown in Table 2, the plate property of selected embodiment preparation is all satisfied national standard and wants to particleboard production index
It asks.Under conditions of the same hot pressing factor, Examples 1 to 2 raw material type is identical, and comparative example 1,2 is it is found that component (b) adds
Dosage is promoted to 0.36% from the 0.18% of wood shavings content, and plate property promotion is smaller, and illustrating that component (b) dosage is in is suitable for water
It is flat.
Compared with comparative example 1, sandwich layer wood shavings are added to the Examples 1 to 5 of component (b), in the condition of the identical hot pressing factor
Under, binding performance is obviously improved in plate, and the material selected in the present embodiment can promote plate property, effect approximation phase
Together.Interior binding performance is to restrict the most key factor of production efficiency, and the raising of binding performance directly illustrates that sandwich layer is viscous in plate
Mixture solidification rate is improved, and improves production efficiency so as to reduce hot pressing time.
After comparative example 1 and embodiment 6 compare it can be found that sandwich layer is added to polyol component, hot pressing time is being reduced
In the case of (be reduced to 5s/mm from hot pressing factor 6s/mm), the interior binding performance of plate is not significantly reduced still, illustrates this
Hot pressing time promotion hot pressing efficiency, raising efficiency about 16% can be reduced by inventing the isocyanate adhesive system being related to.
Embodiment 1 is compared with comparative example 2, since embodiment more than 1 joined FeCl3, internal bond strength is compared to comparison
Example 2 improves about 7.5%, illustrates FeCl3Addition can improve the curing degree of adhesive, and then side light its can be improved
Production efficiency.
Embodiment 7~11
It is increased before mating formation and displays link, that is, after displaying the sealing that wood shavings unit carries out certain time after being glued again
Mat formation, displaying temperature is 50 DEG C, and the hot pressing factor is 6s/mm.7~9 raw material type of embodiment and embodiment 1 are identical, real
Applying PMDI acid value in example 8~9 is 3000ppm；Embodiment 10 and 11 carries out acidification, acid value to PMDI using isobutyryl chloride
For 500ppm, other making sheet design parameters are shown in Table 3, and for remaining process conditions referring to embodiment 1, plate property is shown in Table 4.
Comparative example 3~4
The corresponding making sheet design parameter of comparative example 3 or 4 is shown in Table 3, remaining process conditions is referring to embodiment 7~11, plate
4 can be shown in Table.
3 plate design parameter of table
4 plate property of table
Adhesive precuring degree is studied, is mainly reflected in into its mechanical property after plate, adhesive precuring amount is few, hot pressing
The plate property of preparation can improve.From the variation tendency of IB and SB in table 4 can be seen that 50 DEG C sealing display 1h after, plate
Performance has more apparent lower.Can be seen that in conjunction with IB/SB down ratio be not added with the comparative example 3 of acid compound~
4, performance decline is more significant.The plate of the addition of variety classes acid compound and the PMDI preparation of different acid values, performance
Variation is smaller, illustrates that the addition of acid compound can inhibit the precuring degree of isocyanate adhesive system, improves
The utilization rate of adhesive.
Integrated embodiment 1~11 is with comparative example 1~4 it is found that isocyanate adhesive system according to the present invention is not
In the case where increasing dosage, Wood-based Panel Production efficiency can be improved, reduce adhesive precuring degree.
Embodiment 12
Surface layer wood shavings are arrived in atomization sizing after acrylic aqueous emulsions (solid content 52%) to be added to the water dilution of 3 times of quality
In grain, slab is cold-pressed after sizing, simulates continuous lines precompressed, slab is compressed to pressure maintaining 5- after about 35cm under the same terms
6S is placed on simulation transition machine after taking-up and carries out conveyer belt transition simulation.Simulating slab transitional facility is according to Dieffenbacher
The parameter of offer is adjusted, and belt speed is about 230-240mm/s after debugging, and adjacent conveyor belts are spaced about 60-
65mm, corresponding making sheet parameter are shown in Table 5, and sizing and paving process are referring to embodiment 1.
Embodiment 13
Embodiment 13 uses EVA lotion (solid content 55%), remaining is shown in Table 5 referring to embodiment 12, corresponding making sheet parameter.
Comparative example 5
AddO-on therapy (c), remaining reference embodiment 12 do not carry out comparative example 5, and corresponding making sheet parameter is shown in Table 5.
5 plate design parameter of table
* solid part meter of component (c).
It is shot during test in conveyer belt transition position, sees attached drawing 1,2,3.
Slab in embodiment 12 and embodiment 13 keeps more complete form when passing through adjacent conveyor belts gap,
Slab, without being scattered, collapsing and phenomenon of rupture, illustrate that slab has preferably afterwards component (c) is added during crossing gap
Tack.In comparative example 5, since component (c) not being added, when with identical condition by transmission band gap, slab is not due to having
In gap phenomenon of being scattered of collapsing occurs for standby tack, and will lead to subsequent plate can not normally produce.
Finally it should be noted that above embodiments are only described to the preferred embodiment of the present invention, rather than it is right
The limitation of the scope of the present invention, although the invention is described in detail with reference to the preferred embodiments, the ordinary skill of this field
The all variations and modifications that personnel should be appreciated that modification or equivalent replacement of the technical solution of the present invention are made and make, should all
It falls within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of isocyanate adhesive system, including following components:
(a) polyfunctionality isocyanates and acid compound；
(b) polyalcohol, amines catalyst and optional iron containing compounds；With
Optional (c) water-based emulsion.
2. adhesive composition as described in claim 1, which is characterized in that the polyfunctionality isocyanates is selected from aromatic series polyisocyanate
One of cyanate, aliphatic polyisocyante, araliphatic polyisocyanate and alicyclic polyisocyanates are a variety of；It is preferred that
Aromatic polyisocyanate；More preferable toluene di-isocyanate(TDI), methyl diphenylene diisocyanate and polymethylene polyphenyl are different
One of cyanate is a variety of.
3. adhesive composition as claimed in claim 1 or 2, which is characterized in that the acid compound includes HCl and/or acyl chlorides；
The acyl chlorides includes one of trimethyl-aceyl chloride, paraphthaloyl chloride, Adipoyl Chloride, isobutyryl chloride and positive caprylyl chloride or more
Kind；The dosage of the acid compound is calculated as 200- according to the acid value of component (a) after addition acid compound with HCl
10000ppm, preferably 500-3000ppm.
4. such as any one of claim 1-3 described adhesive system, which is characterized in that the polyalcohol includes that polyether polyols are pure and mild
One of polyester polyol is a variety of, and preferably degree of functionality is that the polyethylene oxide that 2-6 number-average molecular weight is 200-8000 is polynary
Alcohol, more preferable degree of functionality are 3, and number-average molecular weight is the polyethylene oxide polyol of 800-5000；
Preferably, the polyfunctionality isocyanate weight ratio in the component (b) in polyalcohol and component (a) is 0.01-0.2:
1, preferably 0.06-0.12:1.
5. such as any one of claim 1-4 described adhesive system, which is characterized in that the iron containing compounds include ferrous salt and
One of molysite is a variety of, preferably FeCl2、FeSO4、FeCl3、Fe2(SO4)3、Fe(NO3)3, ferric acetyl acetonade, ferrous lactate
With one of ironic citrate or a variety of, more preferable FeCl3And/or Fe2(SO4)3。
6. such as any one of claim 1-5 described adhesive system, which is characterized in that the dosage of the iron containing compounds is with iron
Meter is the 20-2000ppm, preferably 200-1000ppm of polyfunctionality isocyanate weight in component (a).
7. such as any one of claim 1-6 described adhesive system, which is characterized in that the water-based emulsion include PVA lotion,
One of EVA lotion, PVAc lotion, acrylic emulsion and PUD lotion are a variety of.
8. such as any one of claim 1-7 described adhesive system, which is characterized in that the dosage of the water-based emulsion is with solid part
The weight ratio of meter and polyfunctionality isocyanates in component (a) is 0.05-1:1, preferably 0.1-0.5:1.
9. a kind of method that any one of -8 described adhesive systems prepare wood-based plate according to claim 1, includes the following steps:
(1) component (a) is applied to whole substrates, component (b) is applied to sandwich layer, component (c) is applied to surface layer；
It preferably, is to be applied to sandwich layer after 1:1 to 1:5 is mixed according to weight ratio by component (b) and water；
Surface layer is applied to after component (c) and water are mixed according to weight ratio for 1:1 to 1:5；
(2) gained substrate in step (1) is mated formation, hot pressing.
10. a kind of wood-based plate, the wood-based plate includes any one of claim 1-8 described adhesive system.
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