CN108865038A - Isocyanate group wood materials adhesive and its application method - Google Patents
Isocyanate group wood materials adhesive and its application method Download PDFInfo
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- CN108865038A CN108865038A CN201710341295.2A CN201710341295A CN108865038A CN 108865038 A CN108865038 A CN 108865038A CN 201710341295 A CN201710341295 A CN 201710341295A CN 108865038 A CN108865038 A CN 108865038A
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- wood materials
- coupling agent
- isocyanate group
- adhesive
- isocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of isocyanate group wood materials adhesives, include following components：(a) polyisocyanates and/or its derivative, (b) polyamide and (c) coupling agent；The present invention also provides the application methods of above-mentioned adhesive.When wood materials adhesive composition of the invention is used as artificial board adhesive, there is waterproof performance outstanding and excellent mechanical property.
Description
Technical field
The present invention relates to a kind of isocyanate group wood materials adhesive and its application method, in particular to a kind of wooden people
Make plate isocyanate group wood materials adhesive.
Background technique
Currently used wood-based plate is aldehydes adhesive with synthetic adhesive, i.e., Lauxite (UF), phenolic resin (PF),
The adhesive such as melamine formaldehyde resin are " three-aldehyde glue " of representative.These three types of adhesive all use formaldehyde for synthesis material, glue
Connecing product in the production and use process has formaldehyde evolution, is considered as one of major source of room air pollution, pollution week
Phase is long, is difficult to remove at all, annoyings the development of industry of artificial boards always.
The isocyanate adhesive of the considerations of for environmental factor, no aldehyde are more and more widely used in recent years.
In addition to without formaldehyde, there are many more advantages for isocyanates, and such as glue-joint strength height, curing rate is fast, plate excellent physical properties etc..
A large number of studies show that the NCO group as contained by isocyanates can react to form chemistry with the reactive hydrogen in wood materials
Key, therefore use isocyanates that usually there is outstanding waterproof performance, water resistance as plate obtained by wood adhesive
More traditional urea-formaldehyde glue greatly improves.But when being used as outdoor architecture structural panel or floor base material, water resistance still cannot
Reach requirement.To improve water resistance, it usually needs increase the dosage of isocyanates.However, due to isocyanates unit cost compared with
Height, plate glue cost will be greatly improved by increasing glue consumption.
In order to solve the above problem, in the artificial board manufacturing process using traditional urea-formaldehyde glue as adhesive, the prior art is usual
Using the waterproofing agent containing paraffin component.The chemical component of paraffin is that saturation n-alkane almost without any reactivity is excellent
Good hydrophobic substance is considered as best waterproofing agent for a long time.As patent CN 102950429 discloses a kind of waterproof, mould proof
Agent and preparation method thereof, the waterproof, mould inhibitor include the glue being made of paraffin, stearic acid and dodecyl-alpha-D-glucose glycosides
The capsule shells of capsule core and high-molecular compound gelatin and chitosan composition, can effectively reduce the instantaneous absorption speed of wood-based plate；CN
104559828 disclose a kind of emulsion paraffin water repellent used for shaving board, which is main with solid paraffin, stearic acid and water
Raw material, alkyl polyoxyethylene ether and poly- three pear ester are emulsifier, and tripolyphosphate wax is catalyst, and sodium carboxymethylcellulose is gluing
Agent is formed through distribution emulsification saponification, solid content with higher and good waterproof performance at a certain temperature.But exactly
Since paraffin does not have reactivity, so that the addition of waterproofing agent paraffin is also an impediment to the combination between wood material and wood material
Firmness can interfere isocyanates to react with reactive hydrogen in timber, cause to tie especially when the use of isocyanates being adhesive
Close strength reduction.Therefore, it in (height) density fiber board and particieboard production, adds paraffin or increases paraffin dosage often
The mechanical property of product is influenced, the bond strength of product is especially reduced, this has been the theory since Wood-based Panel Production comes out
It is confirmed with practice.
Therefore, the prior art is difficult to solve the wood-based plate waterproof problem using isocyanates as adhesive, it is necessary to develop one
Kind is directed to the waterproof project of wood-based plate isocyanate adhesive.
Summary of the invention
In order to overcome the above-mentioned problems of the prior art, the present invention provides a kind of isocyanate group wood materials bonding
Agent is used as the adhesive of production wood materials, greatly improves the waterproofs such as expansion rate of water absorption and the water absorption rate of produced plate
Property index, while there is excellent mechanical property.
The present invention also provides a kind of application method of isocyanate group wood materials adhesive, the application method is simple
It is easy, it is at low cost.
The technical solutions adopted are as follows for isocyanate group wood materials adhesive provided by the invention：
A kind of isocyanate group wood materials adhesive includes following components：
(a) polyisocyanates and/or its derivative；
(b) polyamide；With
(c) coupling agent.
In the present invention, the polyisocyanates is known in the art, including intramolecular at least contains there are two NCO base
Aromatic series, aliphatic and the alicyclic isocyanate of group.In a preferred embodiment, the polyisocyanates is more methylenes
Quito polyphenyl polyisocyanate, NCO content are preferably 26-32%, more preferable 30-32%, such as ten thousand magnificent chemical groups shares
One of PM-200, PM-400, PM-600 and PM-700 of Co., Ltd, CW20 and CW30 or a variety of.
In the present invention, the derivative of the polyisocyanates is known in the art, including by polyalcohol, polynary
The reaction product of at least one active hydrogen compounds and polyisocyanates including amine, polyacid.Wherein, the polyalcohol can
To be copolymerized ethoxylated polyhydric alcohol selected from polyoxypropylene polyol, polypropylene oxide-ethylene oxide, ethylene oxide polyalcohol, gather in oneself
Ester polyol, polymer polyatomic alcohol, polyolefin polyhydric alcohol, vegetable oil polyol, polytetrahydrofuran polyol and polytetrahydrofuran-
Propylene oxide is copolymerized one or both of ethoxylated polyhydric alcohol or a variety of.
In a preferred embodiment, the polyisocyanate derivative is dihydric alcohol and polymethylene polyphenyl polyisocyanate
The reaction product of cyanate；Wherein, the dihydric alcohol is selected from polyester diol, polyether Glycols, polytetrahydrofuran dihydric alcohol, gathers
Caprolactone dihydric alcohol, silicone glycol, polyoxyethylene glycol (PEG), polyoxypropylene diols, PULLRONIC F68 are total
Dimer diol, polyethylene glycol adipate glycol, polybutylene glyool adipate, polypropylene glycol adipate glycol, poly- fourth
Cyclohexadienediol, one of polycaprolactone diols and polytetrahydrofuran dihydric alcohol (PTMEG) or a variety of.
The number-average molecular weight of the dihydric alcohol is 300~10000, preferably 400~8000, more preferable 500~4000, such as
1000,2000 or 3000.The example of suitable dihydric alcohol include Placcel205 (Japanese Daisel chemical industry Co., Ltd),
CMA-24 (Hua Da Chemical Co., Ltd.), CMA-44 (Hua Da Chemical Co., Ltd.), ODX-218 (Hua Da Chemical Co., Ltd.),
DL-400 (blue star Dong great chemical industry Co., Ltd), DL-1000 (blue star Dong great chemical industry Co., Ltd), PEG-1000
(Zibo is imperial together by (DOW Chemical), PEG-3350 (DOW Chemical), PEA-2000 (Hua Da Chemical Co., Ltd.) and HTPB-4000
Chemical Co., Ltd.), PEBA-1500 (Taiwan Changxing Chemical Co., Ltd.), PHA-2000 (Taiwan Changxing Chemical Co., Ltd.),
One of PEDA-1500 (Taiwan Changxing Chemical Co., Ltd.), PTMEG-1000 (tall and handsome to reach) or a variety of；It is preferred that Placcel
205, one of CMA-24, CMA-44, ODX-218, DL-400, DL-1000, PEG-3350, PEA-2000 and HTPB-4000
Or it is a variety of.
The preparation method of the derivative of polyisocyanates of the present invention is well known to those skilled in the art, such as to
Dihydric alcohol is added in polyisocyanates, the derivative for being kept for 60~70 DEG C prepare polyisocyanates.
Adhesive according to the present invention, it is preferable that the NCO content of the polyisocyanate derivative is 20~30wt%,
It is preferred that 22~30wt%, more preferable 24~30wt%.
In the present invention, the polyisocyanates can be mixed using arbitrary proportion as component with polyisocyanate derivative
(a)。
Adhesive according to the present invention, molecular weight made of the polyamide is preferably reacted as polyacid with polyamine is not
Low molecular polyamides greater than 8000, amine value are 180~1000mg KOH/g, preferably 200~800mg KOH/g, such as 400
Or 600mg KOH/g, be conducive to preferably be reacted with isocyanates, improve Binder Properties.
In the present invention, at least four carbon atom is preferably comprised in the acid molecular structures of the polyacid, may advantageously facilitate institute
Product after the Versamid of generation is reacted with isocyanates has higher toughness, further preferably aliphatic or fragrance
Race's polyacid.
In the present invention, the example of polyacid include adipic acid, succinic acid, glutaric acid, suberic acid, azelaic acid, decanedioic acid,
Decane dicarboxylic, fumaric acid, dimerization and/or trimerized fatty acids, vegetable oil acid (such as ricinoleic acid, cotton oil acid, vegetable seed oleic acid or
Behenic acid etc.) one of or it is a variety of, the example of polyamine includes ethylenediamine, diethylenetriamine, triethylene tetramine, four ethylene five
One of amine, polyethylene polyamine, aminoethyl ethanolamine, aminoethyl piperazine are a variety of.
The example for the low molecular polyamides that polyacid is reacted with polyamine include polyamide 200, polyamide 203,
One of kymene 00, polyamide 6 50, polyamide 6 51, kymene 051, polyamide 400 and polyamide 6 00 are a variety of.
In the present invention, the dosage of the polyamide is preferably 10~40wt% of the dosage of component (a), further preferably
15~35wt%, more preferable 20~30wt%, such as 25wt%.
In the present invention, the coupling agent be preferably selected from silane coupling agent, titanate coupling agent, aluminate coupling agent with
And one of zirconium ester coupling agent or a variety of；
Wherein, the silane coupling agent has Y (CH2)nSiX3General structure, in formula, n=0~3；X is hydrolyzable
Group, including chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group etc.；Y is organo-functional group, including ethylene
Base, amino, epoxy group, methacryloxy, sulfydryl or urea groups.Suitable silane coupling agent includes three second of gamma-amino propyl
Oxysilane (KH-550), gamma-amino propyl trimethoxy silicane (KH-551), γ-(2,3 the third oxygen of epoxy) propyl trimethoxy
Silane, gamma-mercaptopropyltriethoxysilane (KH-580), γ-mercaptopropyl trimethoxysilane (KH-590), N- β-(ammonia second
Base)-γ-aminopropyltriethoxy dimethoxysilane (KH-602), N- β-(aminoethyl)-γ-aminopropyltriethoxy trimethoxy silane
(KH-602), double-[γ-(triethoxysilicane) propyl] tetrasulfide, anilinomethyl triethoxysilane (south big -42 silane),
Vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171) and vinyl three ('beta '-methoxy ethyoxyl)
One of silane (A-172) is a variety of.
The titanate coupling agent has ROO(4-n)Ti(OX-R’Y)nGeneral structure, in formula, n=2 or 3；RO- is
The hydrolyzable lower alkyloxy containing each carbon atom of 1-4, OX- are carboxyl, alkoxy, sulfonic group or phosphorus base；Suitable metatitanic acid
Ester coupling agent includes three isostearic acid isopropyl titanates, three isostearic acid isopropyl titanate compounds, two oleic acid acyl-oxygen of isopropyl
Base (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, three oleic acid acyl-oxygen of isopropyl
Base titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, Di(dioctylpyrophosphato) ethylene titanate,
The chelate solution of Di(dioctylpyrophosphato) ethylene titanate and triethanolamine, two (dioctyl phosphorous of tetra isopropyl
Sour acyloxy) one of titanate esters or a variety of.
The zirconium ester coupling agent is selected from four (triethanolamine) zirconates, sodium lactate zirconium, zirconium ester coupling agent, bis- (lemons
Lemon diethyl phthalate) dipropoxy zirconium chelate, (vinyl-ethyoxyl) zirconate of alkoxy three and three (p-aminophenyl of alkoxy
Oxygroup) one of zirconate or a variety of.
The aluminate coupling agent is selected from aluminium isopropoxide, praseodynium aluminium, isopropoxy distearyl acid acyl-oxygen
One of base Aluminate, isopropoxy distearyl acid acyloxy Aluminate are a variety of.
The dosage of the coupling agent be preferably component (a) weight be 0.5~35wt%, further preferred 1~25wt%,
More preferably 5~20wt%, such as 10wt% or 15wt%.
Other side for achieving the above object, application method provided by the invention adopt the following technical scheme that：
A kind of application method of adhesive, comprises the steps of：
(1) component (a), component (b) and component (c) of adhesive of the invention are uniformly mixed with wood materials；
(2) step (1) mixed raw material is mated formation into the slab of predetermined shape；
(3) slab step (3) obtained carry out it is normal temperature compressed, it is then hot-forming, obtain plate.
In step of the present invention (1), each component of adhesive is mixed with wood materials, wherein above-mentioned mixed mixing
Mode can be the conventional hybrid mode of this field, for example, each component is separately added into wood materials according to the ratio carry out mixing or
Person adds in wood materials after premixing at least two components of described adhesive and mixes；The wood materials can be
Clastic or powdered wood materials；The mixing can carry out in mixing apparatus commonly used in the art, such as mixing plant.
In step (1) of the present invention, the total addition level of adhesive component (a), component (b) and component (c) accounts for wood materials weight
Measure the 1-8wt%, preferably 2-7wt% of ratio.
In step (2) of the invention, mixed raw material is mated formation into the slab of predetermined shape, such as is packed into scheduled
In mold, the process be it is known in the art, which is not described herein again.
It is normal temperature compressed to slab progress in step (3) of the invention, it is then hot-forming；Preferably, exist first
Applying under room temperature makes the thickness of slab reduce 30% or more, then slab is carried out to hot pressing at a temperature of 140-240 DEG C, wherein
Hot pressing pressure (gauge pressure) is preferably 1-5MPa, such as 2 or 4MPa.
Adhesive of the invention has excellent waterproof performance and mechanical property, and polyamide wherein included is in hot pressing
In, primary amino group is reacted with secondary amino group with the NCO on isocyanates on polyamide, generates the polyureas with high cohesion energy, improves plate
Material mechanical property；In addition, unexpectedly, the special polyurea structure hydrone generated being reacted with isocyanates by polyamide and is difficult to
Infiltration, greatly enhances the water resistance of plate.
Further, since introducing coupling agent in adhesive composition, after the completion of sizing, action of coupling agents is in wood materials table
Face causes wooden material surface active site to increase, and activation wooden material surface will make more isocyanic acids in hot pressing
Ester and isocyanates are reacted with the product of polyamide reaction with active site, and firmization is formed between adhesive and wood materials
It learns bond to close, mechanical strength is caused to further increase, simultaneously as gluing oxidant layer and a large amount of chemical bonds of wooden material surface are deposited
Hydrone is difficult to attack, so that plate further has enhanced water resistance.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
The source of polyalcohol and polyisocyanates involved in embodiment and comparative example is as follows：
Polyalcohol：
Placcel 205, polycaprolactone diols, number-average molecular weight 530, Japanese Daisel chemical industry Co., Ltd；
PEG-1000, polyoxyethylene glycol, number-average molecular weight 1000, DOW Chemical；
PEG-3350, polyoxyethylene glycol, number-average molecular weight 3350, DOW Chemical；
CMA-44, polybutylene glyool adipate, number-average molecular weight 2000, Hua Da Chemical Co., Ltd.；
HTPB-4000, polybutadiene diol, number-average molecular weight 4000, Zibo Qilong Chemical Industry Co., Ltd.；
PTMEG-1000, polytetrahydrofuran dihydric alcohol, number-average molecular weight 1000 are tall and handsome to reach；
CMA-24, polyethylene glycol adipate glycol, number-average molecular weight 2000, Hua Da Chemical Co., Ltd.；
Polyisocyanates：
PM-200, poly methylene poly phenyl poly isocyanate (PM-200, ten thousand China's chemistry), NCO content is
30.5-32.0%, 25 DEG C of viscosity are 200cp；
PM-400, poly methylene poly phenyl poly isocyanate (PM-400, ten thousand China's chemistry), NCO content is
30.5-32.0%, 25 DEG C of viscosity are 400cp；
PM-600, poly methylene poly phenyl poly isocyanate (PM-600, ten thousand China's chemistry), NCO content is
30.5-32.0%, 25 DEG C of viscosity are 600cp；
PM-700, poly methylene poly phenyl poly isocyanate (PM-700, ten thousand China's chemistry), NCO content is
30.5-32.0%, 25 DEG C of viscosity are 700cp；
CW-20, polyfunctionality isocyanates and methyl diphenylene diisocyanate mixture (CW-20,
Ten thousand China's chemistry), NCO content 30.5-32.0%, iron divides content≤20ppm；
CW-30, polyfunctionality isocyanates and methyl diphenylene diisocyanate mixture (CW-30,
Ten thousand China's chemistry), NCO content 30.5-32.0%, iron divides content≤30ppm；
The preparation of polyisocyanate derivative
Polyisocyanates is heated to 60~70 DEG C, polyalcohol is added in polyisocyanates under stirring conditions, is protected
60~70 DEG C of temperature reactions are held 2~3 hours up to polyisocyanate derivative.Reaction condition and it the results are shown in Table 1.
1 derivatives reaction condition of table and result
Embodiment 1
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 60g poly methylene poly phenyl poly isocyanate PM-200 (ten thousand magnificent chemical groups shares respectively
Co., Ltd), polyamide 6 51 (Changzhou De Ye Chemical Co., Ltd., 380~450mg/KOH/g of amine value) 24g, silane coupling agent
γ aminopropyltriethoxy silane (KH-550, Guangzhou Zhong Jie Chemical Industry Science Co., Ltd) 0.3g is in beaker, by a spray
Rifle connects air compressor, by above-mentioned three kinds of raw materials successively by stirring 40- in the blender under spray gun for paint penetrating stirring
60s.The sizing of sandwich layer wood shavings is carried out according to same process conditions.Successively according to the surface layer 360g Aspen wood shavings+980g sandwich layer wood shavings+
Wood shavings are mated formation in a 350mm*350mm*100mm mold and are pressed into advance by the ratio of mating formation of the surface layer 360g Aspen wood shavings
Slab, by slab in being pressed into plate on hot press.195-200 DEG C of hot pressing temperature, hot pressing pressure 1.5-2MPa, pressing cycle
200s, plate thickness control is about 18mm.After the completion of compacting, each property of plate is tested according to the method for national standard GB/T-17657 defined
Energy.
Embodiment 2
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs the more benzene of 50g poly methylene poly phenyl poly isocyanate derivative 1#, 10g polymethylene respectively
Quito isocyanate derivates 6#, polyamide 6 51 (Changzhou De Ye Chemical Co., Ltd.) 3g, (the firelight or sunlight chemical industry of Changzhou moral of polyamide 200
Co., Ltd, 230~260mg of amine value KOH/g) 3g, (PN-130, the peaceful coupling agent of Nanjing product have three isostearic acid isopropyl titanates
Limit company) 15g is in beaker, by spray gun connection air compressor, above-mentioned three kinds of raw materials are successively sprayed into stirring by spray gun for paint
40-60s is stirred in blender under state.The sizing of sandwich layer wood shavings is carried out according to same technique.According to the surface layer 360g wood shavings+
The ratio of mating formation of the surface layer 980g sandwich layer wood shavings+360g wood shavings, wood shavings are mated formation in a 350mm*350mm*100mm mold
And it is pressed into slab in advance, by slab in being pressed into plate on hot press.195-200 DEG C of hot pressing temperature, hot pressing pressure 1.5-2MPa, hot pressing
Period 200s, plate thickness control is about 18mm.After the completion of compacting, plate is tested according to the method for national standard GB/T-17657 defined
Each performance.
Embodiment 3
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 30g poly methylene poly phenyl poly isocyanate (Wannate CW20, ten thousand China's chemistry collection respectively
Limited liability company of group), the derivative 7# of 30g poly methylene poly phenyl poly isocyanate, (moral firelight or sunlight chemical industry in Changzhou is limited for polyamide 203
Company, 180~220mg of amine value KOH/g) 12g, aluminium isopropoxide (Nanjing Pin Ning coupling agent Co., Ltd) 6g in beaker,
By a spray gun connect air compressor, Wannate CW20 and polyamide 203 are uniformly mixed, then will by mixture with
40-60s is stirred in the blender that aluminium isopropoxide is successively sprayed under stirring by spray gun for paint.It is carried out according to same technique
The sizing of sandwich layer wood shavings.According to the ratio of mating formation of the surface layer the 360g surface layer wood shavings+980g sandwich layer wood shavings+360g wood shavings, by wood shavings in one
Mated formation in 350mm*350mm*100mm mold and be pressed into slab in advance, by slab in being pressed into plate, hot pressing temperature on hot press
195-200 DEG C, hot pressing pressure 1.5-2MPa, pressing cycle 200s, plate thickness control is about 18mm.After the completion of compacting, according to state
The method for marking GB/T-17657 defined tests each performance of plate.
Embodiment 4
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 40g poly methylene poly phenyl poly isocyanate PM-700 (ten thousand magnificent chemical groups shares respectively
Co., Ltd), 20g poly methylene poly phenyl poly isocyanate derivative 2#, kymene 00 (Changzhou De Ye Chemical Co., Ltd.,
310~320mgKOH/g of amine value) 21g, silane coupling agent γ-mercaptopropyl trimethoxysilane (KH-590, outstanding chemical industry in Guangzhou
Science and Technology Ltd.) 5g, three oleic acid acyloxy titanate esters of isopropyl (PN-105, Nanjing Pin Ning coupling agent Co., Ltd) 15g in
In same beaker, a spray gun is connected into air compressor, is added in spray gun after above-mentioned raw materials are uniformly mixed, stirring is sprayed into
In the blender of state and stir 40-60s.The sizing of sandwich layer wood shavings is carried out according to same technique.According to the surface layer 360g wood shavings+
The ratio of mating formation of the surface layer 980g sandwich layer wood shavings+360g wood shavings, wood shavings are mated formation in a 350mm*350mm*100mm mold
And it is pressed into slab in advance, by slab in being pressed into plate on hot press.195-200 DEG C of hot pressing temperature, hot pressing pressure 1.5-2MPa, hot pressing
Period 200s, plate thickness control is about 18mm.After the completion of compacting, plate is tested according to the method for national standard GB/T-17657 defined
Each performance.
Embodiment 5
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 50g poly methylene poly phenyl poly isocyanate (Wannate CW30, ten thousand China's chemistry collection respectively
Group limited liability company), 10g poly methylene poly phenyl poly isocyanate derivative 3#, (moral firelight or sunlight chemical industry in Changzhou has polyamide 200
Limit company, 230~260mg of amine value KOH/g) 6g, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters (PN-
101, Nanjing Pin Ning coupling agent Co., Ltd) 2g and four (triethanolamine) zirconates (ZR-802, the limited public affairs of the peaceful coupling agent of Nanjing product
Department) 1g is in beaker, by spray gun connection air compressor, above-mentioned three kinds of raw materials are successively sprayed into stirring shape by spray gun for paint respectively
40-60s is stirred in blender under state.The sizing of sandwich layer wood shavings is carried out according to same technique.According to the surface layer 360g wood shavings+980g
The ratio of mating formation of the surface layer sandwich layer wood shavings+360g wood shavings carries out wood shavings mat formation simultaneously in advance in a 350mm*350mm*100mm mold
It is pressed into slab, by slab in being pressed into plate on hot press.195-200 DEG C of hot pressing temperature, hot pressing pressure 1.5-2MPa, pressing cycle
200s, plate thickness control is about 18mm.After the completion of compacting, each property of plate is tested according to the method for national standard GB/T-17657 defined
Energy.
Embodiment 6
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 10g poly methylene poly phenyl poly isocyanate PM-400 (ten thousand magnificent chemical groups shares respectively
Co., Ltd), 50g poly methylene poly phenyl poly isocyanate derivative 4#, polyamide 400 (Changzhou De Ye Chemical Co., Ltd.,
180~220mgKOH/g of amine value) 18g, silane coupling agent vinyl triethoxysilane (A-151, outstanding chemical science and technology in Guangzhou
Co., Ltd) 0.6g is in beaker, by spray gun connection air compressor, above-mentioned raw materials are successively sprayed into stirring shape by spray gun for paint
40-60s is stirred in blender under state.The sizing of sandwich layer wood shavings is carried out according to same technique.According to the surface layer 360g wood shavings+980g
The ratio of mating formation of the surface layer sandwich layer wood shavings+360g wood shavings carries out wood shavings mat formation simultaneously in advance in a 350mm*350mm*100mm mold
It is pressed into slab, by slab in being pressed into plate on hot press.195-200 DEG C of hot pressing temperature, hot pressing pressure 1.5-2MPa, pressing cycle
200s, plate thickness control is about 18mm.After the completion of compacting, each property of plate is tested according to the method for national standard GB/T-17657 defined
Energy.
Embodiment 7
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 40g poly methylene poly phenyl poly isocyanate PM-200 (ten thousand magnificent chemical groups shares respectively
Co., Ltd), 20g poly methylene poly phenyl poly isocyanate derivative 5#, (the limited public affairs of the firelight or sunlight chemical industry of Changzhou moral of kymene 051
Department, 330~370mgKOH/g of amine value) 9g, silane coupling agent N- β-(aminoethyl)-γ-aminopropyltriethoxy trimethoxy silane
(KH-602, Guangzhou Zhong Jie Chemical Industry Science Co., Ltd) 12g connects air compressor in beaker, by a spray gun, will be above-mentioned
Raw material is added in spray gun after being uniformly mixed, and sprays into the blender of stirring and stirs 40-60s.According to same work
Skill carries out the sizing of sandwich layer wood shavings.According to the ratio of mating formation of the surface layer the 360g surface layer wood shavings+980g sandwich layer wood shavings+360g wood shavings, will dig
Flower is mated formation in a 350mm*350mm*100mm mold and is pressed into slab in advance, by slab in being pressed into plate on hot press.Heat
195-200 DEG C of temperature, hot pressing pressure 1.5-2MPa, pressing cycle 200s of pressure, plate thickness control is about 18mm.After the completion of compacting,
Each performance of plate is tested according to the method for national standard GB/T-17657 defined.
Comparative example
Select timber substrate of the moisture content for the Aspen wood shavings of 8-10wt% as plate test.Weigh surface layer Aspen wood shavings
2000g is added in blender, weighs 60g poly methylene poly phenyl poly isocyanate PM-200 (ten thousand magnificent chemical groups shares respectively
Co., Ltd) PM-200 is sprayed into blender by spray gun for paint under stirring and stirs 40-60s.According to same technique
Carry out the sizing of sandwich layer wood shavings.According to the ratio of mating formation of the surface layer the 360g surface layer wood shavings+980g sandwich layer wood shavings+360g wood shavings, by wood shavings
Mated formation in a 350mm*350mm*100mm mold and be pressed into slab in advance, by slab in being pressed into plate on hot press.Hot pressing
195-200 DEG C of temperature, hot pressing pressure 1.5-2MPa, pressing cycle 200s, plate thickness control is about 18mm.After the completion of compacting, press
Each performance of plate is tested according to the method for national standard GB/T-17657 defined.
2 plate test performance comparing result of table
As can be seen from the above table, by the present invention provide isocyanate adhesive composition institute's panel (embodiment 1-7) with
Simple poly methylene poly phenyl poly isocyanate institute panel (comparative example) is compared, and the physical property of plate, including interior combination are strong
Degree, elasticity modulus, static bending strength are obviously improved, especially internal bond strength, are promoted amplitude and are reached 50-80%.In waterproof performance side
Face, providing isocyanate adhesive composition institute's panel (embodiment 1-7) by the present invention, expansion rate of water absorption is simple mostly sub- for 24 hours
The 43-62% of methyl polyphenyl polyisocyanate institute's panel (comparative example), water absorption rate is that simple polymethylene polyphenyl is more for 24 hours
The 46-66% of isocyanates institute panel (comparative example), waterproof performance greatly promote.
Claims (10)
1. a kind of isocyanate group wood materials adhesive, which is characterized in that include following components：
(a) polyisocyanates and/or its derivative；
(b) polyamide；With
(c) coupling agent.
2. isocyanate group wood materials adhesive according to claim 1, which is characterized in that the dosage of the polyamide
For 10~40wt% of component (a) dosage, preferably 15~35wt%, more preferable 20~30wt%；
The dosage of the coupling agent be component (a) dosage 0.5~35wt%, preferably 1~25wt%, more preferably 5~
20wt%.
3. isocyanate group wood materials adhesive according to claim 1 or 2, which is characterized in that the polyamide
It reacts to obtain with polyamine by polyacid, molecular weight is not more than 8000；Amine value be 180~1000mg KOH/g, preferably 200~
800mg KOH/g。
4. isocyanate group wood materials adhesive according to claim 3, which is characterized in that the polyacid contain to
Few 4 carbon atoms.
5. isocyanate group wood materials adhesive described in any one of -4 according to claim 1, which is characterized in that described
Polyisocyanates is poly methylene poly phenyl poly isocyanate, and NCO content is preferably 30~32wt%.
6. isocyanate group wood materials adhesive described in any one of -5 according to claim 1, which is characterized in that
The polyisocyanate derivative is obtained by poly methylene poly phenyl poly isocyanate and diol reaction；Preferably,
The number-average molecular weight of the dihydric alcohol is 300~10000, further preferred 400~8000, more preferable 500~4000.
7. isocyanate group wood materials adhesive according to claim 1 to 6, which is characterized in that described more
In isocyanate derivates, NCO content is 20~30wt%, preferably 22~30wt%, more preferable 24~30wt%.
8. isocyanate group wood materials adhesive described in any one of -7 according to claim 1, which is characterized in that described
Coupling agent be selected from one of silane coupling agent, titanate coupling agent, aluminate coupling agent and zirconium ester coupling agent or a variety of.
9. a kind of application method of such as adhesive of any of claims 1-8, comprises the steps of：
(1) component (a), component (b) and component (c) are uniformly mixed with wood materials；
(2) step (1) mixed raw material is mated formation into the slab of predetermined shape；
(3) slab step (3) obtained carry out it is normal temperature compressed, it is then hot-forming, obtain plate.
10. application method according to claim 9, which is characterized in that in step (3), when normal temperature compressed, make slab thickness
30% or more is reduced, hot pressing temperature is 140-240 DEG C, hot pressing pressure 1-5MPa.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341295.2A CN108865038B (en) | 2017-05-16 | 2017-05-16 | Isocyanate-based wood adhesive and application method thereof |
| PCT/CN2017/085705 WO2018209721A1 (en) | 2017-05-16 | 2017-05-24 | Timber adhesive comprising isocyanate groups and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710341295.2A CN108865038B (en) | 2017-05-16 | 2017-05-16 | Isocyanate-based wood adhesive and application method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN108865038A true CN108865038A (en) | 2018-11-23 |
| CN108865038B CN108865038B (en) | 2020-05-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710341295.2A Active CN108865038B (en) | 2017-05-16 | 2017-05-16 | Isocyanate-based wood adhesive and application method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN108865038B (en) |
| WO (1) | WO2018209721A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667096A (en) * | 2021-09-06 | 2021-11-19 | 湖南省玛芸家居科技有限公司 | Environment-friendly MDI glue and contain its fire prevention formaldehyde-free panel for furniture |
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| CA1107422A (en) * | 1978-07-19 | 1981-08-18 | Wolfgang Reuther | Aqueous isocyanate emulsions for gluing chipboards |
| CN87100284A (en) * | 1987-01-15 | 1988-12-21 | 第一工业制药株式会社 | Produce the method for special-shaped products from plants particles material |
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| CN101657481A (en) * | 2007-02-06 | 2010-02-24 | 诺莱克斯股份公司 | Dual component glue |
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| CN105121492A (en) * | 2013-05-15 | 2015-12-02 | Sika技术股份公司 | Structural polyurethane adhesive |
| TW201612265A (en) * | 2014-08-11 | 2016-04-01 | Lubrizol Advanced Mat Inc | Aqueous copolymer coating compositions for industrial and construction applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2426475T3 (en) * | 2009-07-23 | 2013-10-23 | Basf Se | Adhesives and sealants containing cyclohexandicarboxylic acid derivatives |
| EP2558530A1 (en) * | 2010-04-13 | 2013-02-20 | ExxonMobil Chemical Patents Inc. | Adhesive compositions and methods |
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2017
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- 2017-05-24 WO PCT/CN2017/085705 patent/WO2018209721A1/en active Application Filing
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|---|---|---|---|---|
| GB1036891A (en) * | 1963-01-11 | 1966-07-20 | Grace W R & Co | Improvements in isocyanate-containing adhesives |
| CA1107422A (en) * | 1978-07-19 | 1981-08-18 | Wolfgang Reuther | Aqueous isocyanate emulsions for gluing chipboards |
| CN87100284A (en) * | 1987-01-15 | 1988-12-21 | 第一工业制药株式会社 | Produce the method for special-shaped products from plants particles material |
| CN1201469A (en) * | 1995-11-06 | 1998-12-09 | 帝国化学工业公司 | Polyisocyantates composition |
| CN1206034A (en) * | 1997-07-21 | 1999-01-27 | 贾剑珉 | High-strength flexible structure adhesive |
| CN1671815A (en) * | 2002-07-26 | 2005-09-21 | 三井武田化学株式会社 | Adhesive composition and composite film for soft package material |
| CN101657481A (en) * | 2007-02-06 | 2010-02-24 | 诺莱克斯股份公司 | Dual component glue |
| CN102504750A (en) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | Polyurethane sealant with good initial adhesion |
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| CN113667096A (en) * | 2021-09-06 | 2021-11-19 | 湖南省玛芸家居科技有限公司 | Environment-friendly MDI glue and contain its fire prevention formaldehyde-free panel for furniture |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018209721A1 (en) | 2018-11-22 |
| CN108865038B (en) | 2020-05-08 |
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