CN107227144B - A kind of recombinant material environmentally friendly tannin adhesive and preparation method thereof - Google Patents
A kind of recombinant material environmentally friendly tannin adhesive and preparation method thereof Download PDFInfo
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- CN107227144B CN107227144B CN201710412618.2A CN201710412618A CN107227144B CN 107227144 B CN107227144 B CN 107227144B CN 201710412618 A CN201710412618 A CN 201710412618A CN 107227144 B CN107227144 B CN 107227144B
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention provides a kind of recombinant material environmentally friendly tannin adhesives and preparation method thereof, the adhesive is prepared from the following raw materials in parts by weight: 3-10 parts of modified micro-nano celluloses, 100 parts of water, 40-55 parts of tannin, 1-10 parts of organic modified nano montmorillonites, 1.5-5 parts of fillers, 10-20 parts stress type crosslinking agent, the filler is selected from least one of flour, starch, diatomite, kaolin, bentonite and talcum powder.Adhesive prepared by the present invention is environment-friendly and low-toxicity, free formaldehyde≤0.1g/kg；Total volatile organism≤300g/L, and toughening effect is excellent.
Description
Technical field
The invention belongs to timber to process field of adhesive technology, and in particular to a kind of environmentally friendly tannin adhesive of recombinant material and
Preparation method.
Background technique
Recombinant material (industry is commonly called as " Recombinant Wood ") by veneer bleaching, is dyed using common tree species rotary cut venner as raw material,
Flitch is made by the wet viscous cold pressing of certain way rift grain assembly, artificial veneer is made in slicing.In recombinant material manufacturing process, do not break
All natural such as heat-insulated natural timber, insulation, temperature adjustment, damping has been fully retained in the microstructure and build-in attribute of bad timber
Attribute, overcome the numerous natural defects of artificial fast growing wood, it can be achieved that timber high-value-use.Nearly 30 years, research staff was main
A large amount of research and industrialization development have been carried out around the manufacturing equipment of recombinant material and the functionalization of product.With industry size
Sharply to expand, the R&D work of system relatively lags behind, and recombinant material product still has the problems such as environmental-protecting performance is not high enough and brittleness is big,
Demand of the market to high-quality recombinant material product is lagged far behind, the sound development of recombinant material industry is seriously limited.
CN103878833A (2014-6-25) discloses a kind of manufacturing method of Recombined bamboo fancy veneer, however these sides
Method does not solve the problem of recombinant material flexibility difference, and the high problem of burst size of methanal still has much room for improvement.
Summary of the invention
The present invention provides a kind of environmentally friendly tannin adhesives of recombinant material, have the advantages that environmental protection, content of formaldehyde are low, use
Modified vegetable protein is to prepare biomass emulsion after raw material is grafted with activated monomer, is acted synergistically with micro-nano fiber element, so that glue
Stick toughening effect is excellent.
The technical proposal for solving the technical problem of the invention are as follows:
A kind of environmentally friendly tannin adhesive of recombinant material, the adhesive are prepared from the following raw materials in parts by weight: 3-10 parts
Modified micro-nano cellulose, 100 parts of water, 40-55 parts of tannin, 1-10 parts of organic modified nano montmorillonites, 1.5-5 parts of fillers, 10-
20 parts stress type crosslinking agent,
The filler is selected from least one of flour, starch, diatomite, kaolin, bentonite and talcum powder；
Micro-nano fiber element the preparation method comprises the following steps: the timber or stalk fibre that will remove lignin and hemicellulose carry out
Sour processing forms cellulose paste, and then plus water adjusts stock quality concentration to 1.5-2%, carries out high pressure under 50-150MPa pressure
Homogenisation cycle 2-10 times controls fibre diameter in 10-50nm using the modified formation micro-nano cellulose suspension in surface.
Invention also provides a kind of recombinant material preparation methods of environmentally friendly tannin adhesive, include the following steps:
(1) timber or stalk fibre that remove lignin and hemicellulose the preparation of micro-nano fiber element: are subjected to sour processing
Cellulose paste is formed, then plus water adjusts slurry concentration to 1.5-2%, carries out high-pressure homogeneous circulation 2- under 50-150MPa pressure
10 times, using the modified formation micro-nano cellulose suspension in surface, fibre diameter is controlled in 10-50nm；
(2) host agent synthesizes: pine or Baybery tannin powder being configured to aqueous solution, filtered, pH to 5.0 is adjusted；It will be exfoliated
Above-mentioned tannin aqueous solution stirring is added in stratiform organic modified nano montmorillonite, is warming up to 60-90 DEG C, reacts 30-60min, cooling
Host agent is made to room temperature, the mass ratio of the tannin, water and organic modified nano montmorillonite is 50:100:1-5；
By mixing modified montmorillonite and tannin aqueous solution, there is good expansion in water using montmorillonite
Dispersibility and gelling property, and modified stratiform spacing increases, Interaction between layers power weakens, and surface becomes hydrophobic from hydrophily
Property, between the active group of the reaction in tannin is introduced insertion cheating engaging layer, the interlamellar spacing of tannin macromolecular is made to increase and carry out
Removing improves the physical and mechanical property of tannin adhesive；
(3) stress type crosslinking agent preparation: by mass ratio be 1:0.5-1.5 polyisocyanates and stress modifying agent be added
In reaction vessel, logical N is stirred2Protection heating, is warming up to 50-80 DEG C, reacts 60-180min, obtains performed polymer, is then added and hands over
Join agent, cooling be made stress type crosslinking agent, the mass ratio of the crosslinking agent and performed polymer is 1-3:100；
Isocyanate curing agent is modified using end-block method, it is quickly a large amount of to reduce the two after it contacts host agent
Generation addition and polymerization reaction, extend glue working life, curing agent by thermal stimulus end group unseal generate cross-linking reaction.
(4) glue is prepared: micro-nano fiber element, host agent and filler being uniformly mixed by the parts by weight, addition stress type friendship
Join agent and be uniformly mixed obtained environmentally friendly tannin adhesive, the filler is selected from flour, starch, diatomite, kaolin, bentonite and cunning
At least one of mountain flour.
Preferably, acid reaction variables described in step (1) are that the acid for being 30-60% with mass fraction is mixed with cellulose
Uniformly, it is stirred to react at 40-80 DEG C 1-3 hours, the acid is sulfuric acid or hydrochloric acid, and the mass ratio of the acid and cellulose is
10-15:1。
Preferably, cellulose paste is carried out the pretreatment of low temperature high-energy ultrasonic, specific work before step (1) mesohigh homogeneous
Skill is to add slurry into ultrasonic reactor, leads to 5-10 DEG C of cooling circulating water, opens supersonic generator, and ultrasonic power is arranged
300-1000W, supersonic frequency 20kHz, ultrasonic time 15-60min.Cellulose paste progress low temperature high energy is surpassed before high-pressure homogeneous
Sound preconditioning is conducive to further decrease fiber size, and big fiber blocking, reduces homogenization cycles when so as to alleviate homogeneous.
Preferably, surface modification technology described in step (1) are as follows: add water to prepare the micro-nano fiber element after homogenization
For the slurry of mass concentration ratio 1-2%, the silane coupling agent of the 1-3% of stock quality is added, is carried out in ultrasonic reactor in situ
Ultrasonic reaction, the silane coupling agent are KH550, KH560, KH570 at least one.
It is further preferred that the original position ultrasonic reaction condition are as follows: lead to 30-50 DEG C of circulator bath, be passed through nitrogen, airflow rate is arranged
For 5-30ml/min, after deoxygenation 3-10min, supersonic generator is opened, ultrasonic power 600-900W, supersonic frequency are set
20kHz, ultrasonic time 5-30min.
The present invention is right in conjunction with nanometer toughening mechanism by research micro-nano fiber element surface topography, crystal form and characteristics of functional groups
Micro-nano fiber element surface is modified, and is solved the problems, such as that micro-nano fiber element is compounded with adhesive host agent and is mixed, develops
Modified micro-nano fiber element suspension and toughening adhesives；Terminal isocyanate groups closing theory, curing mechanism are studied, with recombinant material system
Technique is made to combine, be made stress type crosslinking agent, make adhesive working life >=3 hour, and realize and press Shi Shouwen in recombinant material
Degree, the deblocking of Pressure stimulation end group generate cross-linking reaction, achieve the purpose that flitch glue molding.
Preferably, the preparation method of exfoliated stratiform organic modified nano montmorillonite described in step (2) is that will cover to take off
Native original soil is configured to suspension, and standing sedimentation takes out upper layer suspension, the NaCl crystal for accounting for dry ground quality 6% is added, at 60 DEG C
Heating stirring 2h, through suction filtration, washing, drying, it is levigate obtain sodium-based montmorillonite, weighed sodium-based montmorillonite is scattered in deionized water
In, stirring at normal temperature 0.5h, and adjust the pH value of mixed liquor weighs intercalator cetyl trimethylammonium bromide, wiring solution-forming,
Enter in montmorillonite suspension liquid, constant temperature stirring a period of time stands, and after obtained flocculent deposit is filtered, washed, then uses alcohol
Washing 3 times is finally putting into drier at 80 DEG C dry 3h, takes out and grinds obtained organo montmorillonite, the sodium-based montmorillonite,
The mass ratio of deionized water and cetyl trimethylammonium bromide is 1:10:0.1-0.5.
Preferably, polyisocyanates described in step (3) is selected from polymethylene multi-phenenyl isocyanate, six methines two
At least one of isocyanates and methyl diphenylene diisocyanate；It is described stress modifying agent be polyethylene glycol, polytetrahydrofuran
At least one of two pure and mild polyetheramines, the crosslinking agent are kind of a silane with organo-functional group, general formula Y-R-SiX3, X and Y
It is the different active group of two class response characteristics, X is chloro, methoxyl group, ethyoxyl, methoxyethoxy or acetoxyl group, and Y is
Vinyl, amino, epoxy group or methacryloxy.X is hydrolyzable groups, and when hydrolysis generates silanol Si (HO)3, can be with
It combines and is chemically crosslinked with the group of inorganic matter；Y is organo-functional group, is orientated to organic resin surface, can with it is organic
Group (such as-OH) combines, and generates hydrophobic chemical key.
The invention has the benefit that
1, the adhesive prepared by the present invention is environment-friendly and low-toxicity, free formaldehyde≤0.1g/kg；Total volatile organism≤
300g/L。
2, the present invention improves the toughness of adhesive using modified micro-nano cellulose, using ultrasonic reaction means in situ to micro-
Cellulose surface of receiving is modified, and is solved the problems, such as that micro-nano fiber element is compounded with adhesive host agent and is mixed.
3, the adhesive prepared by the present invention is easy to use, closes theoretical and curing mechanism using terminal isocyanate groups, makes
Cross-linking reaction is generated by temperature, the deblocking of Pressure stimulation end group when obtaining recombinant material pressing, achievees the purpose that flitch glue molding.
Specific embodiment
Invention is further described in detail with reference to embodiments.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
The preparation of 1 organic modified nano montmorillonite of embodiment
100g original montmorillonoid soil is configured to suspension, standing sedimentation takes out upper layer suspension, and addition accounts for dry ground 6g's
NaCl crystal through suction filtration, washing, drying, levigate obtains 102g sodium-based montmorillonite, weighed 20g sodium in 60 DEG C of heating stirring 2h
Base montmorillonite is scattered in 200g deionized water, stirring at normal temperature 0.5h, and adjusts the pH value of mixed liquor, and 6g is claimed to take intercalator 16
Alkyl trimethyl ammonium bromide, wiring solution-forming pour into montmorillonite suspension liquid, and constant temperature stirring a period of time stands, obtained wadding
After shape precipitating is filtered, washed, then with ethanol wash 3 times, it is finally putting into drier at 80 DEG C dry 3h, takes out grinding system
Obtain organo montmorillonite.
The preparation of the environmentally friendly tannin adhesive of embodiment 2
(1) 250g mass fraction the preparation of micro-nano fiber element: is added in the 20g timber for removing lignin and hemicellulose
For in 30% sulfuric acid, be uniformly mixed, the sour processing formation cellulose paste of progresss in 2 hours be stirred to react at 60 DEG C, then plus
700g water adjusts slurry concentration to 2%, carries out high-pressure homogeneous circulation 8 times under 100MPa pressure, it is even to add 20g KH550 silane
Join agent, forms micro-nano cellulose suspension after ultrasonic reaction in situ is carried out in ultrasonic reactor, control fibre diameter exists
40nm；The original position ultrasonic reaction condition are as follows: lead to 40 DEG C of circulator baths, be passed through nitrogen, setting airflow rate is 20ml/min, row
After oxygen 5min, supersonic generator is opened, ultrasonic power 800W, supersonic frequency 20kHz, ultrasonic time 20min are set.
(2) host agent synthesizes: 50g Baybery tannin powder addition 100g being configured to aqueous solution, filters, adjusts pH to 5.0；
Above-mentioned tannin aqueous solution stirring is added in the exfoliated stratiform organic modified nano montmorillonite of 3g, 60 DEG C is warming up to, reacts 60min,
It is cooled to room temperature obtained host agent；
It (3) stress the preparation of type crosslinking agent: reaction vessel is added in 10g hexamethylene-diisocyanate and 5g polyethylene glycol
In, stir logical N2Protection heating, is warming up to 60 DEG C, reacts 100min, obtains 15g performed polymer, and 0.3g crosslinking agent, drop is then added
Temperature be made stress type crosslinking agent, the crosslinking agent be the silane with organo-functional group, general formula Y-R-SiX3, X and Y are two classes
The different active group of response characteristic, X are chloro, and Y is vinyl；
(4) glue is prepared: 5g micro-nano fiber element, 155g host agent and 3g starch being uniformly mixed by the parts by weight, are added
15g stress the uniformly mixed obtained environmentally friendly tannin adhesive of type crosslinking agent.
Institute's produced environment friendly tannin adhesive is used to prepare recombinant decorative material performance, detects the recombinant decorative material performance of compacting,
Dipping and stripping: side does not have peeling；Static bending strength (longitudinal direction) is 58.4MPa, and bending elastic modulus (longitudinal direction) is small to be
6630MPa；Nail-holding ability: being parallel or substantially in parallel to glue-line plate face is 1490N, is perpendicular to or substantially perpendicular to glue-line plate face
1400N, end face 1090N；Burst size of methanal is 0.1mg/L.
Embodiment 3
(1) 300g mass fraction the preparation of micro-nano fiber element: is added in the 20g timber for removing lignin and hemicellulose
For in 40% sulfuric acid, be uniformly mixed, the sour processing formation cellulose paste of progresss in 2 hours be stirred to react at 60 DEG C, then plus
700g water adjusts slurry concentration to 2%, carries out high-pressure homogeneous circulation 10 times under 50MPa pressure, it is even to add 10g KH560 silane
Join agent, forms micro-nano cellulose suspension after ultrasonic reaction in situ is carried out in ultrasonic reactor, control fibre diameter exists
10nm；The original position ultrasonic reaction condition are as follows: lead to 30 DEG C of circulator baths, be passed through nitrogen, setting airflow rate is 50ml/min, row
After oxygen 10min, supersonic generator is opened, ultrasonic power 600W, supersonic frequency 20kHz, ultrasonic time 5min are set.
(2) host agent synthesizes: 50g Baybery tannin powder addition 100g being configured to aqueous solution, filters, adjusts pH to 5.0；
Above-mentioned tannin aqueous solution stirring is added in the exfoliated stratiform organic modified nano montmorillonite of 1g, 80 DEG C is warming up to, reacts 40min,
It is cooled to room temperature obtained host agent；
It (3) stress the preparation of type crosslinking agent: reaction vessel is added in 10g methyl diphenylene diisocyanate and 15g polyetheramine
In, stir logical N2Protection heating, is warming up to 50 DEG C, reacts 180min, obtains 25g performed polymer, and 0.5g crosslinking agent, drop is then added
Temperature be made stress type crosslinking agent, the crosslinking agent be the silane with organo-functional group, general formula Y-R-SiX3, X and Y are two classes
The different active group of response characteristic, X are methoxyl group, and Y is methacryloxy；
(4) glue is prepared: 10g micro-nano fiber element, 151g host agent and 5g bentonite are uniformly mixed by the parts by weight,
20g is added stress the uniformly mixed obtained environmentally friendly tannin adhesive of type crosslinking agent.
Institute's produced environment friendly tannin adhesive is used to prepare recombinant decorative material performance, detects the recombinant decorative material performance of compacting,
Dipping and stripping: side does not have peeling；Static bending strength (longitudinal direction) is 59.5MPa, and bending elastic modulus (longitudinal direction) is small to be
6636MPa；Nail-holding ability: being parallel or substantially in parallel to glue-line plate face is 1495N, is perpendicular to or substantially perpendicular to glue-line plate face
1413N, end face 1098N；Burst size of methanal is 0.1mg/L.
Embodiment 4
(1) 200g mass fraction the preparation of micro-nano fiber element: is added in the 20g timber for removing lignin and hemicellulose
For in 60% hydrochloric acid, be uniformly mixed, the sour processing formation cellulose paste of progresss in 2 hours be stirred to react at 60 DEG C, then plus
700g water adjusts slurry concentration to 2%, carries out high-pressure homogeneous circulation 2 times under 150MPa pressure, it is even to add 30g KH570 silane
Join agent, forms micro-nano cellulose suspension after ultrasonic reaction in situ is carried out in ultrasonic reactor, control fibre diameter exists
50nm；The original position ultrasonic reaction condition are as follows: lead to 50 DEG C of circulator baths, be passed through nitrogen, setting airflow rate is 30ml/min, row
After oxygen 3min, supersonic generator is opened, ultrasonic power 900W, supersonic frequency 20kHz, ultrasonic time 30min are set.
(2) host agent synthesizes: 50g Baybery tannin powder addition 100g being configured to aqueous solution, filters, adjusts pH to 5.0；
Above-mentioned tannin aqueous solution stirring is added in the exfoliated stratiform organic modified nano montmorillonite of 5g, 90 DEG C is warming up to, reacts 30min,
It is cooled to room temperature obtained host agent；
(3) stress type crosslinking agent preparation: 10g polymethylene multi-phenenyl isocyanate and 8g polytetrahydrofuran diol are added
Enter in reaction vessel, stirs logical N2Protection heating, is warming up to 80 DEG C, reacts 60min, obtains 18g performed polymer, be then added
0.18g crosslinking agent, cooling be made stress type crosslinking agent, the crosslinking agent be the silane with organo-functional group, general formula Y-R-
SiX3, X and Y is the different active group of two class response characteristics, and X is methoxyethoxy, and Y is amino；
(4) glue is prepared: 10g micro-nano fiber element, 160g host agent and 1.5g diatomite are mixed by the parts by weight
Even, 10g is added stress the uniformly mixed obtained environmentally friendly tannin adhesive of type crosslinking agent.
Institute's produced environment friendly tannin adhesive is used to prepare recombinant decorative material performance, detects the recombinant decorative material performance of compacting,
Dipping and stripping: side does not have peeling；Static bending strength (longitudinal direction) is 60.2MPa, and bending elastic modulus (longitudinal direction) is small to be
6645MPa；Nail-holding ability: being parallel or substantially in parallel to glue-line plate face is 1503N, is perpendicular to or substantially perpendicular to glue-line plate face
1412N, end face 1096N；Burst size of methanal is 0.1mg/L.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of environmentally friendly tannin adhesive of recombinant material, which is characterized in that the adhesive by following parts by weight raw material system
At: 3-10 parts of micro-nano fiber elements, 100 parts of water, 40-55 parts of tannin, 1-10 parts of organic modified nano montmorillonites, 1.5-5 parts of fillers,
10-20 parts stress type crosslinking agent,
The filler is selected from least one of flour, starch, diatomite, kaolin, bentonite and talcum powder；
Micro-nano fiber element the preparation method comprises the following steps: the timber or stalk fibre that will remove lignin and hemicellulose carry out at acid
Reason forms cellulose paste, and then plus water adjusts stock quality concentration to 1.5-2%, carries out high-pressure homogeneous under 50-150MPa pressure
Circulation 2-10 times controls fibre diameter in 10-50nm using the modified formation micro-nano fiber element suspension in surface；
The preparation method of the organic modified nano montmorillonite is that original montmorillonoid soil is configured to suspension, and standing sedimentation takes out
Upper layer suspension is added and accounts for the NaCl crystal of dry ground quality 6%, in 60 DEG C of heating stirring 2h, through suction filtration, washing, drying, levigate
Sodium-based montmorillonite is obtained, weighed sodium-based montmorillonite is scattered in deionized water, stirring at normal temperature 0.5h, and adjusts the pH of mixed liquor
Value, weighs intercalator cetyl trimethylammonium bromide, and wiring solution-forming pours into montmorillonite suspension liquid, when constant temperature stirs one section
Between stand, after obtained flocculent deposit is filtered, washed, then with ethanol wash 3 times, be finally putting into drier at 80 DEG C
Dry 3h, takes out to grind organo montmorillonite is made, the sodium-based montmorillonite, deionized water and cetyl trimethylammonium bromide
Mass ratio is 1:10:0.1-0.5；
It is described stress type crosslinking agent the preparation method comprises the following steps: by mass ratio be 1:0.5-1.5 polyisocyanates and stress modifying agent
It is added in reaction vessel, stirs logical N2Protection heating, is warming up to 50-80 DEG C, reacts 60-180min, obtains performed polymer, then plus
Enter crosslinking agent, cooling be made stress type crosslinking agent, the mass ratio of the crosslinking agent and performed polymer is 1-3:100.
2. the environmentally friendly tannin adhesive of recombinant material as described in claim 1, which is characterized in that the acid reaction variables are to use matter
The acid that amount score is 30-60% is uniformly mixed with cellulose, is stirred to react at 40-80 DEG C 1-3 hours, it is described it is sour for sulfuric acid or
The mass ratio of hydrochloric acid, the acid and cellulose is 10-15:1.
3. the method for preparing the environmentally friendly tannin adhesive of recombinant material described in claim 1, which is characterized in that the preparation method
Include the following steps:
(1) preparation of micro-nano fiber element: the timber or stalk fibre that remove lignin and hemicellulose are subjected to sour processing and formed
Cellulose paste, then plus water adjusts slurry concentration to 1.5-2%, carries out high-pressure homogeneous circulation 2-10 under 50-150MPa pressure
It is secondary, using the modified formation micro-nano cellulose suspension in surface, fibre diameter is controlled in 10-50nm；
(2) host agent synthesizes: pine or Baybery tannin powder being configured to aqueous solution, filtered, pH to 5.0 is adjusted；By exfoliated stratiform
Above-mentioned tannin aqueous solution stirring is added in organic modified nano montmorillonite, is warming up to 60-90 DEG C, reacts 30-60min, be cooled to room
The obtained host agent of temperature, the mass ratio of the tannin, water and organic modified nano montmorillonite are 50:100:1-5；
(3) stress type crosslinking agent preparation: by mass ratio be 1:0.5-1.5 polyisocyanates and stress modifying agent be added reaction
In container, logical N is stirred2Protection heating, is warming up to 50-80 DEG C, reacts 60-180min, obtains performed polymer, and crosslinking is then added
Agent, cooling be made stress type crosslinking agent, the mass ratio of the crosslinking agent and performed polymer is 1-3:100；
(4) glue is prepared: micro-nano fiber element, host agent and filler being uniformly mixed by the parts by weight, addition stress type crosslinking agent
It is uniformly mixed and environmentally friendly tannin adhesive is made, the filler is selected from flour, starch, diatomite, kaolin, bentonite and talcum powder
At least one of.
4. preparation method as claimed in claim 3, which is characterized in that acid reaction variables described in step (1) are with quality point
The acid that number is 30-60% is uniformly mixed with cellulose, is stirred to react at 40-80 DEG C 1-3 hours, and the acid is sulfuric acid or salt
The mass ratio of acid, the acid and cellulose is 10-15:1.
5. preparation method as claimed in claim 3, which is characterized in that before step (1) mesohigh homogeneous by cellulose paste into
The pretreatment of row low temperature high-energy ultrasonic, concrete technology are to add slurry into ultrasonic reactor, lead to 5-10 DEG C of cooling circulating water, open
Ultrasonic power 300-1000W, supersonic frequency 20kHz, ultrasonic time 15-60min is arranged in supersonic generator.
6. preparation method as claimed in claim 3, which is characterized in that surface modification technology described in step (1) are as follows: by homogeneous
Treated, and micro-nano fiber element adds water to be formulated as the slurry of mass concentration 1-2%, and the silane coupled of the 1-3% of stock quality is added
Agent, carries out ultrasonic reaction in situ in ultrasonic reactor, and the silane coupling agent is KH550, KH560, KH570 at least one.
7. preparation method as claimed in claim 6, which is characterized in that the original position ultrasonic reaction condition are as follows: logical 30-50 DEG C is followed
Ring water-bath, is passed through nitrogen, and setting airflow rate is 5-30ml/min, after deoxygenation 3-10min, opens supersonic generator, setting
Ultrasonic power 600-900W, supersonic frequency 20kHz, ultrasonic time 5-30min.
8. preparation method as claimed in claim 3, which is characterized in that polyisocyanates described in step (3) is selected from more methylenes
At least one of Quito phenyl isocyanate, hexamethylene-diisocyanate and methyl diphenylene diisocyanate；It is described stress
Modifying agent is at least one of polyethylene glycol, polytetrahydrofuran diol and polyetheramine, and the crosslinking agent is that kind has organic functional
The silane of group, general formula Y-R-SiX3, X and Y is the different active group of two class response characteristics, and X is chloro, methoxyl group, ethoxy
Base, methoxyethoxy or acetoxyl group, Y are vinyl, amino, epoxy group or methacryloxy.
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| CN107227144B true CN107227144B (en) | 2019-05-21 |
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| CN108841255A (en) * | 2018-05-25 | 2018-11-20 | 东阳市天齐科技有限公司 | A kind of VAE method of producing waterproof coating material |
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| CN103459542A (en) * | 2010-09-14 | 2013-12-18 | 韩国科学技术院 | Adhesive composition comprising tannin, polyethylene glycol, and water, lower alcohol or mixture thereof |
| CN106336839A (en) * | 2016-09-21 | 2017-01-18 | 德华兔宝宝装饰新材股份有限公司 | Preparation method of adhesive for recombined material |
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| CN103459542A (en) * | 2010-09-14 | 2013-12-18 | 韩国科学技术院 | Adhesive composition comprising tannin, polyethylene glycol, and water, lower alcohol or mixture thereof |
| CN106336839A (en) * | 2016-09-21 | 2017-01-18 | 德华兔宝宝装饰新材股份有限公司 | Preparation method of adhesive for recombined material |
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| "Enhancement of mechanical strength of particleboard using environmentally friendly pine(Pinus pinaster L.) tannin adhesives with cellulose nanofibers";Juqing Cui等;《Annals of Forest Science》;20141231;第72卷;第27-28页 |
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