CN110283563A - A kind of modified composite adhesive and preparation method thereof - Google Patents
A kind of modified composite adhesive and preparation method thereof Download PDFInfo
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- CN110283563A CN110283563A CN201910593266.4A CN201910593266A CN110283563A CN 110283563 A CN110283563 A CN 110283563A CN 201910593266 A CN201910593266 A CN 201910593266A CN 110283563 A CN110283563 A CN 110283563A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6446—Proteins and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- 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
- C09J175/04—Polyurethanes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3063—Magnesium sulfate
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- C—CHEMISTRY; METALLURGY
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of modified composite adhesives, are prepared by the raw material of following parts by weight: 40-50 parts of modified polyurethane, 50-60 parts of curing agent, 15-20 parts of acetone, 30-36 parts of filler, 3-5 parts of chitosan, 1-2 parts of o-phthalic acid dibutyl ester；The invention also discloses the preparation methods of the modified composite adhesive, include the following steps: step S1, acetone, curing agent and chitosan are mixed to get first component；Step S2, filler and modified polyurethane are mixed to get second component；Step S3, first component and second component are mixed, adds o-phthalic acid dibutyl ester, stirs evenly, modified composite adhesive is made.The present invention is not introduced into any substance containing aldehyde during preparing modified composite adhesive；By the modification to bonding material polyurethane so that adhesive has excellent bonding strength, in addition, in the present invention filler and additions can be improved the bonding strength of adhesive, reduce the viscosity of adhesive, be more easier covering with paint.
Description
Technical field
The invention belongs to adhesive technology fields, and in particular, to a kind of modified composite adhesive and preparation method thereof.
Background technique
Sticking and the effects of cohesion, two or more product or material can be made to link together by interface
Natural or synthesis a, organic or inorganic substance, is referred to as adhesive.With growing stronger day by day for wood-based panel industry,
Wood composite material is widely used in the fields such as house construction and household.For Wood composite material, the use of adhesive
It is essential.
It is built and the big back closely related to human life such as household however, being widely used in house in Wood composite material
Under scape, the adhesive that existing preparation method obtains is still based on three formaldehyde resins, i.e. urea-formaldehyde resin adhesive, phenolic resin gluing
Agent and melamine resin adehsive stick agent.Three-aldehyde glue itself has free aldehyde and free phenol, can release in production, transport, use process
Harmful substance is put, it is larger to the body harm of people.
Summary of the invention
The purpose of the present invention is to provide a kind of modified composite adhesives and preparation method thereof, prepare modified composite adhesive
During be not introduced into any substance containing aldehyde, obtained modification composite adhesive can thoroughly solve the problems, such as free aldehyde release；
By the modification to bonding material polyurethane, adhesive provided by the invention has excellent bonding strength, in addition, in the present invention
Filler and addition can be improved the bonding strength of adhesive, reduce the viscosity of adhesive, make to cover with paint, lacquer, colour wash, etc. and be more easier；Chitosan
The antibacterial ability that can also improve adhesive is added, improves the service life of adhesive.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of modified composite adhesive, is prepared by the raw material of following parts by weight: 40-50 parts of modified polyurethane, solidification
50-60 parts of agent, 15-20 parts of acetone, 30-36 parts of filler, 3-5 parts of chitosan, 1-2 parts of o-phthalic acid dibutyl ester；
The modified composite adhesive is prepared by following steps:
Step S1, acetone is added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48
DEG C, curing agent and chitosan are added inwards, are stirred 10-12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18-20min, obtains second component；
Step S3, first component and second component are mixed, 300r/min stirs 5-7min, and it is pungent to add phthalic acid two
Rouge improves mixing speed to 450r/min, continues to stir 26-28min, modified composite adhesive is made.
Further, the curing agent includes alum, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride
It is 10:0.8-1:16-20 mixing according to mass ratio；The alum, magnesium sulfate, ammonium chloride are nanometer grade powder, ruler
Very little is 10-100nm.
Further, it according to mass ratio is 1 that the filler, which is nano-titanium dioxide, nano-cellulose, basalt fibre:
0.5-0.6:0.1-0.2 is mixed；The nano-titanium dioxide, nano-cellulose, basalt fibre are nanometer grade powder,
Partial size is 15-120nm.
Further, the modified polyurethane is prepared by the following method:
(1) degreased wool chestnut powder and distilled water are mixed with the ratio of 1:20,55 DEG C is warming up to, with the sodium hydroxide of 1mol/L
Solution adjusts pH value and is stirred to react 3h to 9.5-9.8, is centrifuged, takes supernatant, then the hydrochloric acid solution tune of 1mol/L is used at 50 DEG C
It saves pH value and stirs 6min to 4.2-4.5, then be adjusted to neutrality with the sodium hydroxide solution of 1mol/L, hair chestnut protein liquid is made, it is standby
With；
(2) in the split type four mouthfuls of reaction flasks for being furnished with thermometer, condensing unit, blender, 120mL acetone is placed,
10.3g polyethylene glycol is first added, mixed liquor is warming up to 103-106 DEG C, the vacuum dehydration 4h at 103-106 DEG C；
(3) system is cooled to 50 DEG C, and turn on agitator, 100r/min is at the uniform velocity stirred, and 6.7g is added during stirring
Isophorone diisocyanate adds 1-2 drop dibutyl tin dilaurate, is warming up to 68 DEG C, constant temperature is stirred to react 66min；
(4) continue 2, the 2- dihydromethyl propionic acid that 11.6g is added to system, be warming up to 78 DEG C and be stirred to react 3h, be cooled to
60 DEG C, 1.2g triethylamine is added, stirs 30min；
(5) system is moved in ice-water bath, is instilled 35mL maos of chestnut protein liquids using constant pressure funnel, when control is added dropwise
Between be 45-50min, drip off rear high-speed stirred reaction 70min, synthetic product used into acetone washing to remove unreacted list
Body obtains modified polyurethane.
A kind of preparation method of modified composite adhesive, includes the following steps:
Step S1, acetone is added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48
DEG C, curing agent and chitosan are added inwards, are stirred 10-12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18-20min, obtains second component；
Step S3, first component and second component are mixed, 300r/min stirs 5-7min, and it is pungent to add phthalic acid two
Rouge improves mixing speed to 450r/min, continues to stir 26-28min, modified composite adhesive is made.
Beneficial effects of the present invention:
For composite adhesive of the invention using modified polyurethane as bonding material, the modified polyurethane is by hair chestnut
Protein molecular modified polyurethane prepolymer obtains, and modified polyurethane obtained is stable faint yellow lotion；Polyurethane prepolymer
The cross-linking modified hair chestnut albumen of body is grafted hair chestnut protein molecular chain on the end group (- NCO) of base polyurethane prepolymer for use as, so that modified poly-
There is only urethane bonds in urethane structure, and there is also more branches, drop significantly so as to cause the crystallinity of adhesive
It is low；Meanwhile the reticular structure of the short peptide chain crosslinking adult form of line style can be improved the heat of modified polyurethane by base polyurethane prepolymer for use as
Stability；Furthermore collagen hydrolysate crosslinks reaction and forms complicated reticular structure, intermolecular cohesion enhancing,
So that modified polyurethane solid content is high and without precipitating；
The curing agent that composite adhesive of the invention uses is the solidification of alum, magnesium sulfate, ammonium chloride three compounding
Agent, alum are ackd salt, and contain metal aluminium ion, acidic environment are provided in adhesive solidification process, aluminium ion is again
The solidification that flocculation accelerates adhesive occurs with modified polyurethane molecule；It is added after magnesium sulfate, magnesium sulfate water suction becomes band
The magnesium sulfate crystallization of water accelerates modified polyurethane solidification, the degree of cross linking of modified polyurethane is increased, to improve compound gluing
The adhesivity and water resistance of agent；Three component composite curing agents, can be improved the bonding strength of composite adhesive；
The filler that composite adhesive of the invention uses includes nano-titanium dioxide, nano-cellulose, basalt fibre, is received
Rice cellulose has compared with polyhydroxy, and hydroxyl activity is higher, can enhance the hydrophily of adhesive, and adhesive is made to be easy to adsorb air
In hydrone, and form hydrogen bond, to enhance the glue performance of adhesive, enhance the intensity and ageing properties of adhesive；
It when basalt fibre is filled into adhesive, diffuses into one another, permeate between the phase molecule chain of interface, tangling forms bonding layer, load
It is transmitted by the effects of physical absorption of glue surfaces, friction, basalt fibre can play the role of reinforcement；Meanwhile
It is orientated in shearing field with the anisotropic basalt fibre of silicate property, reduces the viscosity of system, in high temperature
Under the action of temperature field, basalt fibre and modified polyurethane strand generate crosslinking, cause partially modified polyurethane molecular can
Between being inserted into basalt fibre, fibre lay-up structure sheaf is strutted, so that compound viscosity declines, therefore under high temperature action, it is multiple
It closes adhesive to be easier to be cured phenomenon, is conducive to reduce squeeze time；
The present invention is not introduced into any substance containing aldehyde during preparing modified composite adhesive, the compound gluing of obtained modification
Agent can thoroughly solve the problems, such as free aldehyde release；By the modification to bonding material polyurethane, adhesive provided by the invention
With excellent bonding strength, in addition, in the present invention filler and addition can be improved the bonding strength of adhesive, reduce gluing
The viscosity of agent is more easier covering with paint；The addition of chitosan can also improve the antibacterial ability of adhesive, improve making for adhesive
Use the service life.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff all other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
A kind of modified composite adhesive, is prepared by the raw material of following parts by weight: 40-50 parts of modified polyurethane, solidification
50-60 parts of agent, 15-20 parts of acetone, 30-36 parts of filler, 3-5 parts of chitosan, 1-2 parts of o-phthalic acid dibutyl ester；
The curing agent includes alum, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride according to quality it
Than being mixed for 10:0.8-1:16-20；Alum, magnesium sulfate, ammonium chloride are nanometer grade powder, having a size of 10-100nm；
Alum is ackd salt, and contains metal aluminium ion, provides acidic environment in adhesive solidification process, aluminium from
With modified polyurethane molecule the solidification that flocculation accelerates adhesive occurs for son again；It is added after magnesium sulfate, magnesium sulfate water suction becomes
Accelerate modified polyurethane solidification at the magnesium sulfate crystallization with water, the degree of cross linking of modified polyurethane is increased, to improve compound
The adhesivity and water resistance of adhesive；Three component composite curing agents, can be improved the bonding strength of composite adhesive；
It according to mass ratio is 1:0.5-0.6 that the filler, which is nano-titanium dioxide, nano-cellulose, basalt fibre:
0.1-0.2 is mixed；Nano-titanium dioxide, nano-cellulose, basalt fibre are nanometer grade powder, partial size 15-
120nm；
Nano-cellulose has compared with polyhydroxy, and hydroxyl activity is higher, can enhance the hydrophily of adhesive, keeps adhesive easy
Hydrone in absorption air, and forms hydrogen bond, to enhance the glue performance of adhesive, enhance adhesive intensity and
Ageing properties；When basalt fibre is filled into adhesive, diffuses into one another, permeates between the phase molecule chain of interface, tangling forms glue
Connect layer, load is transmitted by the effects of physical absorption, friction of glue surfaces, and basalt fibre can play reinforcement work
With；Meanwhile there is the anisotropic basalt fibre of silicate property to be orientated in shearing field, make the viscosity drop of system
Low, under the action of temperature field, basalt fibre and modified polyurethane strand generate crosslinking, lead to partially modified poly- ammonia
Ester molecule is inserted between basalt fibre, and fibre lay-up structure sheaf struts, so that compound viscosity declines, therefore is made in high temperature
Under, composite adhesive is easier to be cured phenomenon, is conducive to reduce squeeze time；
The modified polyurethane is prepared by the following method:
(1) degreased wool chestnut powder and distilled water are mixed with the ratio of 1:20,55 DEG C is warming up to, with the sodium hydroxide of 1mol/L
Solution adjusts pH value and is stirred to react 3h to 9.5-9.8, is centrifuged, takes supernatant, then the hydrochloric acid solution tune of 1mol/L is used at 50 DEG C
It saves pH value and stirs 6min to 4.2-4.5, then be adjusted to neutrality with the sodium hydroxide solution of 1mol/L, hair chestnut protein liquid is made, it is standby
With；
(2) in the split type four mouthfuls of reaction flasks for being furnished with thermometer, condensing unit, blender, 120mL acetone is placed,
10.3g polyethylene glycol is first added, mixed liquor is warming up to 103-106 DEG C, the vacuum dehydration 4h at 103-106 DEG C；
(3) system is cooled to 50 DEG C, and turn on agitator, 100r/min is at the uniform velocity stirred, and 6.7g is added during stirring
Isophorone diisocyanate adds 1-2 drop dibutyl tin dilaurate, is warming up to 68 DEG C, constant temperature is stirred to react 66min；
(4) continue 2, the 2- dihydromethyl propionic acid that 11.6g is added to system, be warming up to 78 DEG C and be stirred to react 3h, be cooled to
60 DEG C, 1.2g triethylamine is added, stirs 30min；
(5) system is moved in ice-water bath, is instilled 35mL maos of chestnut protein liquids using constant pressure funnel, when control is added dropwise
Between be 45-50min, drip off rear high-speed stirred reaction 70min, synthetic product used into acetone washing to remove unreacted list
Body obtains modified polyurethane；
The modified polyurethane being prepared is faint yellow emulsion form；By the cross-linking modified hair chestnut albumen of base polyurethane prepolymer for use as,
Hair chestnut protein molecular chain is grafted on the end group (- NCO) of base polyurethane prepolymer for use as, there is only carbamates in its structure
Key, there is also more branches, substantially reduce so as to cause the crystallinity of adhesive；Meanwhile base polyurethane prepolymer for use as is by line style
Short peptide chain is crosslinked the reticular structure of adult form, can be improved the thermal stability of modified polyurethane；Furthermore collagen hydrolysate is sent out
Raw cross-linking reaction and form complicated reticular structure, intermolecular cohesion enhancing, so that modified polyurethane solid content is high and without heavy
It forms sediment；
The preparation method of the modified composite adhesive, includes the following steps:
Step S1, acetone is added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48
DEG C, curing agent and chitosan are added inwards, are stirred 10-12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18-20min, obtains second component；
Step S3, first component and second component are mixed, 300r/min stirs 5-7min, and it is pungent to add phthalic acid two
Rouge improves mixing speed to 450r/min, continues to stir 26-28min, modified composite adhesive is made.
Embodiment 1
A kind of modified composite adhesive, is prepared by the raw material of following parts by weight: 40 parts of modified polyurethane, curing agent 50
Part, 15 parts of acetone, 30 parts of filler, 3 parts of chitosan, 1 part of o-phthalic acid dibutyl ester；
The curing agent includes alum, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride according to quality it
Than being mixed for 10:0.8:16；
It according to mass ratio is 1:0.5:0.1 mixed that the filler, which is nano-titanium dioxide, nano-cellulose, basalt fibre,
Conjunction is made；
The modified composite adhesive is prepared by following steps:
Step S1, acetone being added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42 DEG C,
Curing agent and chitosan are added inwards, are stirred 10min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18min, obtains second component；
Step S3, first component and second component being mixed, 300r/min stirs 5min, o-phthalic acid dibutyl ester is added,
Mixing speed is improved to 450r/min, continues to stir 26min, modified composite adhesive is made.
Embodiment 2
A kind of modified composite adhesive, is prepared by the raw material of following parts by weight: 45 parts of modified polyurethane, curing agent 55
Part, 18 parts of acetone, 33 parts of filler, 4 parts of chitosan, 1.5 parts of o-phthalic acid dibutyl ester；
The curing agent includes alum, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride according to quality it
Than being mixed for 10:0.9:18；
It according to mass ratio is 1:0.5:0.1 mixed that the filler, which is nano-titanium dioxide, nano-cellulose, basalt fibre,
Conjunction is made；
The modified composite adhesive is prepared by following steps:
Step S1, acetone being added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 45 DEG C,
Curing agent and chitosan are added inwards, are stirred 11min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 19min, obtains second component；
Step S3, first component and second component being mixed, 300r/min stirs 6min, o-phthalic acid dibutyl ester is added,
Mixing speed is improved to 450r/min, continues to stir 27min, modified composite adhesive is made.
Embodiment 3
A kind of modified composite adhesive, is prepared by the raw material of following parts by weight: 50 parts of modified polyurethane, curing agent 60
Part, 20 parts of acetone, 36 parts of filler, 5 parts of chitosan, 2 parts of o-phthalic acid dibutyl ester；
The curing agent includes alum, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride according to quality it
Than being mixed for 10:1:20；
It according to mass ratio is 1:0.6:0.2 mixed that the filler, which is nano-titanium dioxide, nano-cellulose, basalt fibre,
Conjunction is made；
The modified composite adhesive is prepared by following steps:
Step S1, acetone is added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48
DEG C, curing agent and chitosan are added inwards, are stirred 12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 20min, obtains second component；
Step S3, first component and second component being mixed, 300r/min stirs 7min, o-phthalic acid dibutyl ester is added,
Mixing speed is improved to 450r/min, continues to stir 28min, modified composite adhesive is made.
Following performance survey is carried out to the embodiment 1-3 composite adhesive being prepared and common commercial polyurethane adhesive
Examination:
(1) it solid content and viscosity test: is tested according to GB/T 2793-1995 using weight method；Quality is weighed respectively
It for the adhesive sample of m0, is laid in the tinfoil of constant weight, at 100 DEG C, dry to constant weight, quality m1 is counted as the following formula
Calculate solid content=m1/m0*100%；Prepolymer viscosity is measured using Ubbelohde viscometer, each sample is measured in parallel three times, takes it
Average value, test result is as follows table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Commercially available adhesive | |
| Solid content/% | 38.16 | 39.33 | 40.51 | 30.02 |
| Viscosity/mPas | 1328 | 1367 | 1305 | 2214 |
It is found that the solid content for the adhesive that embodiment 1-3 is prepared is greater than 38.16%, viscosity is less than 1328mPas,
Compared to commercial polyurethane adhesive (solid content 30.02%, viscosity 2214mPas), the compound gluing that the present invention is prepared
Agent has high solid content and low viscosity, the excellent performance of obtained adhesive；
(2) Plywood Shear-strength is tested: adhesive veneer prepares, and is by veneer drying made of poplar to moisture content
4.5% or so veneer, is cut into the small veneer that breadth is 300*300 (mm), carries out sanding processing to its surface；Made from testing
Lauxite is cooled to modest viscosity.First same veneer two sides is glued with brush, adhesive is made to be evenly distributed on list
Plate surface, every face resin added are 15g；Veneer after sizing, which must carry out displaying for certain time, just can be carried out hot pressing, purpose
It is the generation of plate bursting phenomenon in order to prevent, assembly time is about 30min；Veneer after displaying is according between adjacent two layers veneer
The mutually perpendicular principle arrangement of texture；The veneer being glued is placed between the veneer that two pieces are not glued, marshalling is put into heat
Hot pressing, hot pressing temperature 120, hot pressing pressure 1-2MPa, hot pressing time 1mm/min, assembly time 30min are carried out in press；Test specimen
It saws and makes according to GB/T 9846.7-2004 " 7 part of glued board-the: the saw system of test specimen ", size: long 99-101mm, wide 24-
26mm, shear plane 25x25mm test shear strength, test result is as follows table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Commercially available adhesive | |
| Shear strength/MPa | 1.33 | 1.38 | 1.35 | 1.05 |
As seen from the above table, the shear strength of the glued board for the composite adhesive bonding that embodiment 1-3 is prepared reaches
1.33MPa or more, relative to commercially available adhesive (1.05MPa), shear strength is obviously improved, and illustrates that the present invention is prepared into
The glue performance of the modification composite adhesive arrived is good, bonding strength is high.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (5)
1. a kind of modified composite adhesive, which is characterized in that be prepared by the raw material of following parts by weight: modified polyurethane 40-
50 parts, 50-60 parts of curing agent, 15-20 parts of acetone, 30-36 parts of filler, 3-5 parts of chitosan, 1-2 parts of o-phthalic acid dibutyl ester；
The modified composite adhesive is prepared by following steps:
Step S1, acetone being added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48 DEG C,
Curing agent and chitosan are added inwards, are stirred 10-12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18-20min, obtains second component；
Step S3, first component and second component are mixed, 300r/min stirs 5-7min, adds o-phthalic acid dibutyl ester, mentions
High mixing speed continues to stir 26-28min, modified composite adhesive is made to 450r/min.
2. a kind of modified composite adhesive according to claim 1, which is characterized in that the curing agent includes aluminum sulfate
Ammonium, magnesium sulfate, ammonium chloride, alum, magnesium sulfate, ammonium chloride are 10:0.8-1:16-20 mixing according to mass ratio；It is described
Alum, magnesium sulfate, ammonium chloride are nanometer grade powder, having a size of 10-100nm.
3. a kind of modified composite adhesive according to claim 1, which is characterized in that the filler is nanometer titanium dioxide
Titanium, nano-cellulose, basalt fibre are mixed according to mass ratio for 1:0.5-0.6:0.1-0.2；The nano-silica
Changing titanium, nano-cellulose, basalt fibre is nanometer grade powder, partial size 15-120nm.
4. a kind of modified composite adhesive according to claim 1, which is characterized in that the modified polyurethane is by such as lower section
Method preparation:
(1) degreased wool chestnut powder and distilled water are mixed with the ratio of 1:20,55 DEG C is warming up to, with the sodium hydroxide solution of 1mol/L
It adjusts pH value to be stirred to react 3h to 9.5-9.8, be centrifuged, take supernatant, then adjusts pH with the hydrochloric acid solution of 1mol/L at 50 DEG C
Value stirs 6min to 4.2-4.5, then is adjusted to neutrality with the sodium hydroxide solution of 1mol/L, and hair chestnut protein liquid is made, spare；
(2) equipped with thermometer, condensing unit, blender split type four mouthfuls of reaction flasks in, place 120mL acetone, first plus
Enter 10.3g polyethylene glycol, mixed liquor is warming up to 103-106 DEG C, the vacuum dehydration 4h at 103-106 DEG C；
(3) system is cooled to 50 DEG C, and turn on agitator, 100r/min is at the uniform velocity stirred, and 6.7g different Buddhist is added during stirring
That ketone diisocyanate, adds 1-2 drop dibutyl tin dilaurate, is warming up to 68 DEG C, constant temperature is stirred to react 66min；
(4) continue 2, the 2- dihydromethyl propionic acid that 11.6g is added to system, be warming up to 78 DEG C and be stirred to react 3h, be cooled to 60 DEG C,
1.2g triethylamine is added, stirs 30min；
(5) system is moved in ice-water bath, is instilled 35mL maos of chestnut protein liquids using constant pressure funnel, control time for adding is
45-50min drips off rear high-speed stirred reaction 70min, synthetic product is used acetone washing to remove unreacted monomer, is obtained
To modified polyurethane.
5. a kind of preparation method of modified composite adhesive, which comprises the steps of:
Step S1, acetone being added in reaction kettle, opens stirring, mixing speed is set as 300r/min, is warming up to 42-48 DEG C,
Curing agent and chitosan are added inwards, are stirred 10-12min, are obtained first component；
Step S2, filler is added in modified polyurethane, 300r/min is stirred 18-20min, obtains second component；
Step S3, first component and second component are mixed, 300r/min stirs 5-7min, adds o-phthalic acid dibutyl ester, mentions
High mixing speed continues to stir 26-28min, modified composite adhesive is made to 450r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910593266.4A CN110283563A (en) | 2019-07-03 | 2019-07-03 | A kind of modified composite adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910593266.4A CN110283563A (en) | 2019-07-03 | 2019-07-03 | A kind of modified composite adhesive and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100581A (en) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111531660A (en) * | 2020-05-09 | 2020-08-14 | 中国林业科学研究院木材工业研究所 | Low-formaldehyde impregnated bond paper facing artificial board and preparation method thereof |
| CN114989385A (en) * | 2022-05-16 | 2022-09-02 | 广州市聚科聚氨酯有限公司 | Modified isocyanate and preparation method thereof |
-
2019
- 2019-07-03 CN CN201910593266.4A patent/CN110283563A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100581A (en) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111100581B (en) * | 2019-12-02 | 2020-11-06 | 福建农林大学 | Full-bio-based adhesive and preparation method and application thereof |
| CN111531660A (en) * | 2020-05-09 | 2020-08-14 | 中国林业科学研究院木材工业研究所 | Low-formaldehyde impregnated bond paper facing artificial board and preparation method thereof |
| CN111531660B (en) * | 2020-05-09 | 2022-02-08 | 中国林业科学研究院木材工业研究所 | Low-formaldehyde impregnated bond paper facing artificial board and preparation method thereof |
| CN114989385A (en) * | 2022-05-16 | 2022-09-02 | 广州市聚科聚氨酯有限公司 | Modified isocyanate and preparation method thereof |
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