CN105542676B - It is a kind of using nano oxidized cellulose slurries as starch adhesive of parent and preparation method thereof - Google Patents

It is a kind of using nano oxidized cellulose slurries as starch adhesive of parent and preparation method thereof Download PDF

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CN105542676B
CN105542676B CN201610051053.5A CN201610051053A CN105542676B CN 105542676 B CN105542676 B CN 105542676B CN 201610051053 A CN201610051053 A CN 201610051053A CN 105542676 B CN105542676 B CN 105542676B
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starch
oxidized cellulose
nano oxidized
parts
slurries
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CN105542676A (en
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黄自知
胡云楚
袁利萍
冯斯宇
卿彦
吴义强
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Central South University of Forestry and Technology
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Central South University of Forestry and Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/02Cellulose; Modified cellulose
    • C09J101/04Oxycellulose; Hydrocellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00Preparation of derivatives of starch
    • C08B31/18Oxidised starch
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a kind of starch adhesive using nano oxidized cellulose slurries as parent, in parts by weight, include the raw material of following component:100 parts of oxygenation efficiency are 5%~30% nano oxidized cellulose slurries, 10~40 parts of starch, 2~5 parts of oxidants, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax.The preparation method of the present invention:First prepare the nano oxidized cellulose slurries that oxygenation efficiency is 5%~30%, starch and 2~5 oxidants are added in batches in the nano oxidized cellulose slurries of preparation again, stabilizer, preservative and emulsified wax are added after being sufficiently stirred, each component is stirred well at 50~70 DEG C to be uniformly dispersed, that is, obtains the starch adhesive.The starch adhesive bonding strength of the present invention is high, water-tolerant.The preparation method of the present invention avoids solvent displacement and drying process, drastically reduce the area energy consumption, reduces labor intensity.

Description

A kind of starch adhesive and its preparation using nano oxidized cellulose slurries as parent Method
Technical field
The present invention relates to a kind of adhesive and preparation method thereof, more particularly to one kind is using nano oxidized cellulose slurries as mother Starch adhesive of body and preparation method thereof.
Background technology
With the appearance of environmental law and the enhancing of people's health consciousness, country is waved free formaldehyde in acetals adhesive The limitation of hair amount is more and more stricter.Wood processing field generally uses at present " three-aldehyde glue " (i.e. Lauxite, phenolic resin and Melamine-formaldehyde resin adhesive sticks agent) substantial amounts of formaldehyde is discharged during production and use, cause environmental pollution and endanger Evil public health.Therefore, it will be research emphasis from now on to develop non-toxic, environmental friendly based Wood Adhesives.
Starch adhesive as environmentally friendly natural glue increasingly by the extensive concern of researcher, starch with Its aboundresources, it is cheap, easy to use the advantages that and using asepsis environment-protecting as bright spot, turn into the timber of most potentiality to be exploited With one of natural glue.But in place of amylan also has its limitation, the gluing intensity and water-fast property of amylan are bad.In order to The good amylan of processability, has been disclosed for certain methods so far.It is (open in Chinese invention patent application prospectus Number:CN101760148A in), propose cornstarch strengthening its paintability and intensity by oxidation reaction.In Chinese invention Patent application prospectus (publication number:The A of CN 104817981) in, propose to add borax, odium stearate, phosphorus in starch Sour tributyl and Nano-meter SiO_22Colloidal sol, because each component mutually blending effect improves the intensity of gluing.
In recent years, nano-cellulose has caused many concerns, Nanowire as a kind of new renewable nano material The diameter of element is tieed up about in 1nm~100nm, can disperse to form stable colloid in water.It is not only basic with cellulose Structure and performance, the also characteristic with nano particle, there is good macroscopic quantum tunneling dimensional effect, skin effect and quantum Dimensional effect, because its unique property makes nano micro crystal cellulose obtain extensively should in fields such as papermaking, weaving, fine chemistry industries With.Also there is correlative study using corresponding performance of the nano-cellulose as additive enhancing adhesive.In Chinese invention patent Ublic specification of application (publication number:The A of CN 103013436) in propose using nano-cellulose as modifying agent enhancing soybean protein Gluing intensity.In Chinese invention patent application prospectus (publication number:CN 103266536 A) in propose be gelatinized Added in cationic starch glue in the Nanocrystalline Cellulose Colloid prepared using microcrystalline cellulose powder as raw material and prepare one kind The good Cypres of high intensity, stability.By adding nano micro crystal cellulose modified starch adhesive, it is obtained preferably Gluing intensity or water resistance, but still can be with improvements in the presence of some.Use modifying nanometer cellulose starch as described above In glue preparation process, using the microcrystal nanometer cellulose powder first prepared as raw material, on the one hand, the system of nano-cellulose It is usually the slurries for first obtaining its nano-cellulose during standby, containing substantial amounts of solvent, and in the process being concentrated and dried Need to consume substantial amounts of energy;On the other hand, for receiving in microcrystal nanometer cellulose drying process is prepared using string Form, the performance of rice fiber have large effect, cause the reduction of its quantum size effect, are added to strong to gluing in amylan The humidification of degree is limited.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of water resistance is good, gluing is strong The high starch adhesive using nano oxidized cellulose slurries as parent is spent, and energy consumption is low, step is simply with nano oxidized Cellulose slurries are the preparation method of the starch adhesive of parent.
In order to solve the above technical problems, technical scheme proposed by the present invention is:
A kind of starch adhesive using nano oxidized cellulose slurries as parent, in parts by weight, including following component Raw material:
100 parts of oxygenation efficiency be 5%~30% nano oxidized cellulose slurries, 10~40 parts of starch, 2~5 parts of oxidants, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax.Wherein oxygenation efficiency is hydroxyl in nano-cellulose The quantity of oxidation accounts for the percentage of the quantity of total hydroxyl, and nano oxidized cellulose and non-oxidation nanometer cellulose form certain match somebody with somebody Than strengthening starch adhesive.
Above-mentioned starch adhesive, it is preferred that the solid content of the nano oxidized cellulose slurries is 8%~12%.
Above-mentioned starch adhesive, it is preferred that the fibre length in the nano oxidized cellulose slurries is 1~100nm Oxycellulose mass fraction be 35%~70%;The oxycellulose mass fraction that fibre length is 100~1000nm is 20%~50%;The oxycellulose mass fraction that fibre length is 1 μm~10mm is 10%~15%.
Above-mentioned starch adhesive, it is preferred that the oxidant is H2O2Or/and NaClO;The stabilizer is polyethylene Glycol;The preservative is ammonium pentaborate.
The inventive concept total as one, the present invention also provide a kind of starch using nano oxidized cellulose slurries as parent The preparation method of gluing, comprises the following steps:
(1) 8~12 parts of pulp boards are taken, are added in 80~100 parts of sulfuric acid solutions, the shear agitation at a temperature of 50~55 DEG C After 1~3h, add 1~2 part of oxidant and continue 0.5~1.0h of shear agitation reaction;200~1000 parts of water are eventually adding to terminate Reaction, product will be obtained and dialysed to pH=1~5, the nano oxidized cellulose slurries that oxygenation efficiency is 5%~30%;
(2) 100 parts of nano oxidized cellulose slurries for taking step (1) to obtain, add in batches 10~40 parts of starch and 2~ 5 parts of oxidants, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax are added after being sufficiently stirred, Each component is stirred well at 50~70 DEG C to be uniformly dispersed, that is, obtains the shallow lake using nano oxidized cellulose slurries as parent Powder adhesive.
Above-mentioned preparation method, it is preferred that in the step (2), add the specific steps of starch and oxidant in batches For:10%~15% of 5%~10% and oxidant quality of starch quality in proportioning is added for the first time, is filled at 50~70 DEG C Divide stirring gelatinization reaction 0.5~1h;Second add 30~40% and oxidant quality of starch quality in proportioning 40%~ 50%, it is sufficiently stirred 0.5~1h at 50~70 DEG C;Third time adds 50%~65% and oxidant of starch quality in proportioning The 35%~50% of quality, 0.5~1h is sufficiently stirred at 50~70 DEG C.
Above-mentioned preparation method, it is preferred that the solid content for the nano oxidized cellulose slurries that the step (1) obtains is 8%~12%;The oxycellulose mass fraction that fibre length is 1~100nm in the nano oxidized cellulose slurries is 35%~70%;The oxycellulose mass fraction that fibre length is 100~1000nm is 20%~50%;Fibre length is 1 μ M~10mm oxycellulose mass fraction is 10%~15%.
Above-mentioned preparation method, it is preferred that the oxidant H2O2Or/and NaClO;The stabilizer is macrogol; The preservative is ammonium pentaborate.
Above-mentioned preparation method, it is preferred that in the step (1), the mass concentration of sulfuric acid solution is 20%~60%;Cut Cutting speed degree is 2000~5000rpm.
The nano oxidized cellulose slurries that oxygenation efficiency is 5%~30% are obtained by above-mentioned steps (1), in follow-up step Suddenly nano-cellulose is by further aoxidizing in (2), and nano oxidized cellulose oxidation rate is 10% in the adhesive finally obtained ~50%.
The present invention after partial oxidation reaction, forms alditol acidic group and carboxyl, such as formula (1) institute based on nano-cellulose Show, nano oxidized cellulose can utilize alditol acidic group and carboxyl to make with starch by the effective crosslinking of esterification formation strength With so as to be advantageous to improve the glue-joint strength and water resistance of adhesive.
Compared with prior art, the advantage of the invention is that:
(1) present invention directly prepares nano-cellulose using nano oxidized cellulose slurries as parent strengthens starch adhesive, Solvent displacement and the drying process in prepared by nano-cellulose are avoided, energy consumption is drastically reduce the area, reduces labor intensity;Together When, part of sulfuric acid when reservation prepares nano-cellulose can effectively save money as the catalyst in starch oxidation process Source, reduce pollution.
(2) present invention is combined using sulphuric acid hydrolysis and mechanical shearing and the nano oxygen chemical fibre with certain length distribution is made Tie up plain slurries strengthens amylan for parent, can be sufficiently reserved the quantum size effect of nano-cellulose, and and can gives full play to not With the humidification of length nano-cellulose, its enhancing effect to gluing intensity has been ensured.
(3) present invention is strengthened using nano-cellulose, and the combination of nano oxidized cellulose and oxidized starch, Neng Gouyou Effect improves the compatibility and bond strength of cellulose and starch.
(4) present invention adds starch in nano oxidized cellulose slurries in batches, and it is aoxidized with suitable oxidizing agent, By this technical combinations of two, reunion and coagulation phenomenon of the starch in slurries are effectively prevent, improves starch adhesive Stability.
(5) present invention is added portionwise after starch carries out gelatinization reaction and has carried out sufficient emulsification to nano oxidized cellulose, Add the stability and wet strength of starch adhesive, in addition the addition of emulsified wax be also beneficial to top layer formed it is appropriate hydrophobic Layer, enhance the water resistance of starch adhesive.On the one hand stabilizer polyvinyl alcohol can effectively extend the Storage period of adhesive, this is Due to containing hydrophilic and hydrophobic group in polyvinyl alcohol molecule, protective colloid action can be played after being dissolved in water, is wrapped in starch Grain surface, hydroxyl shielding between particle is got up, makes dispersion stable, another aspect polyvinyl alcohol makes starch granules uniformly divide Dissipate, effectively prevent reunion and coagulation phenomenon of the starch in slurries, improve the stability of starch adhesive.The boron of preservative five Sour ammonium has antisepsis, while the molecule is also beneficial to dispersing starch particles, improves system stability.Between each component mutually Coordinate, produce compound synergy, effectively improve the stability of starch adhesive.
(6) present invention uses oxygenation efficiency as shallow lake that 5%~30% nano oxidized cellulose slurries are that parent is prepared Powder adhesive has the advantages that bonding strength height, water-tolerant.
Embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or Person can pass through product made from known method.
Embodiment 1:
A kind of starch adhesive of the invention using nano oxidized cellulose slurries as parent, include the original of following component Material:100 grams of oxygenation efficiency are 10% nano oxidized cellulose slurries (solid content 8%), 10 grams of starch, 2 gram mass concentration are 30% Oxidant H2O2, 0.2 gram of stabilizer polyvinyl alcohol, 0.1 gram of preservative ammonium pentaborate and 1 gram of emulsified wax;Nano oxidized cellulose In nanofiber length be 1~100nm content be 40%;The content that nanofiber length is 100~1000nm is 45%; Fibre length is that 1 μm~10mm content is 15%.
The preparation method using nano oxidized cellulose slurries as the starch adhesive of parent of the present embodiment, including following step Suddenly:
(1) 8 grams of pulp boards are weighed, it is in 20% sulfuric acid solution to add 80 gram mass concentration, is stirred in 50 DEG C of temperature down cuts 1h (shear rate 2000rpm) is mixed, then adds the oxidant H that 1 gram mass concentration is 30%2O2It is anti-to continue shear agitation Answer 0.5h;300 grams of water terminating reactions are eventually adding, the product of acquisition is fitted into bag filter, dialyse is to pH=5, solid content 8%th, oxygenation efficiency is 10% nano oxidized cellulose slurries;Nanofiber length is distributed in the nano oxidized cellulose slurries:1 ~100nm, 40%;100~1000nm, 45%;1 μm~10mm, 15%.
(2) 100 grams of nano oxidized cellulose slurries for taking step (1) to obtain, 10 grams of starch and 2 gram masses are added in batches Concentration is 30% oxidant H2O2, 0.5 gram of starch and 0.2 gram of oxidant quality are added for the first time, and gelatinization is sufficiently stirred at 50 DEG C React 0.5h;Second 3 grams of starch and 0.8 gram of oxidant, 0.5h is sufficiently stirred at 50 DEG C;Third time adds 6.5 grams of starch With 1 gram of oxidant, 0.5h is sufficiently stirred at 50 DEG C;It is then respectively adding 0.2 gram of stabilizer polyvinyl alcohol, 0.1 gram of preservative Ammonium pentaborate and 1 gram of emulsified wax;Each component is stirred well at 50 DEG C to be uniformly dispersed, fully react, and is obtained to aoxidize fibre Tie up the starch adhesive that plain slurries are parent.
Sanding is carried out to moisture content 4.5% or so, breadth 300mm × 300mm veneers surface;Received manufactured in the present embodiment Rice oxycellulose slurries are that the starch adhesive of parent by resin added is 300g/m2Uniformly it is applied to veneer surface;Then it is pre- Precompressed 2min under press;It is again 3MPa in thermal pressure, hot pressing time carries out hot pressing under the conditions of being 1mm/min.
The glued board water resistance of above-mentioned preparation is measured by GB/T9846-2004II class glued board standards;According to GB/ T9846-2004II class glued board standards, (with reference to the sample preparation of GB/T17657-1999 standards) glued board is measured using puller system Bonding strength, as a result as shown in table 1.
Embodiment 2:
A kind of starch adhesive of the invention using nano oxidized cellulose slurries as parent, include the original of following component Material:100 grams of oxygenation efficiency be 15% nano oxidized cellulose slurries (solid content 10%), 20 grams of starch, 5 grams of oxidant NaClO, 0.5 gram of stabilizer polyvinyl alcohol, 0.2 gram of preservative ammonium pentaborate and 0.5 gram of emulsified wax;Nanometer in nano oxidized cellulose The content that fibre length is 1~100nm is 47%;The content that nanofiber length is 100~1000nm is 40%;Fibre length Content for 1 μm~10mm is 13%.
The preparation method using nano oxidized cellulose slurries as the starch adhesive of parent of the present embodiment, including following step Suddenly:
(1) 10 grams of pulp boards are weighed, it is in 40% sulfuric acid solution to add 90 gram mass concentration, is stirred in 55 DEG C of temperature down cuts 1h (shear rate 2000rpm) is mixed, 1 gram of oxidant NaClO is then added and continues shear agitation reaction 1.0h;It is eventually adding 500 grams of water terminating reactions, the product of acquisition is fitted into bag filter, and dialyse is to pH=4, solid content 10%, oxygenation efficiency 15% nano oxidized cellulose slurries;Nanofiber length is distributed in the nano oxidized cellulose slurries:1~100nm, 47%;100~1000nm, 40%;1 μm~10mm, 13%.
(2) 100 grams of nano oxidized cellulose slurries for taking step (1) to obtain, 20 grams of starch and 5 grams of oxidations are added in batches Agent NaClO, 2 grams of starch and 0.75 gram of oxidant quality are added for the first time, gelatinization reaction 0.5h is sufficiently stirred at 60 DEG C;Second Secondary 8 grams of starch and 2.5 grams of oxidants, 0.5h is sufficiently stirred at 60 DEG C;Third time adds 10 grams of starch and 1.75 grams of oxidants, 0.5h is sufficiently stirred at 60 DEG C;It is then respectively adding 0.5 gram of stabilizer polyvinyl alcohol, 0.2 gram of preservative ammonium pentaborate and 0.5 Gram emulsified wax, each component is stirred well at 60 DEG C and is uniformly dispersed, fully reacts, is obtained with nano oxidized cellulose slurries For the starch adhesive of parent.
Sanding is carried out to moisture content 4.5% or so, breadth 300mm × 300mm veneers surface;Received manufactured in the present embodiment Rice oxycellulose slurries are that the starch adhesive of parent by resin added is 300g/m2Uniformly it is applied to veneer surface;Then it is pre- Precompressed 2min under press;It is again 3MPa in thermal pressure, hot pressing time carries out hot pressing under the conditions of being 1mm/min.
The glued board water resistance of above-mentioned preparation is measured by GB/T9846-2004II class glued board standards;According to GB/ T9846-2004II class glued board standards, (with reference to the sample preparation of GB/T17657-1999 standards) glued board is measured using puller system Bonding strength, as a result as shown in table 1.
Embodiment 3:
A kind of starch adhesive of the invention using nano oxidized cellulose slurries as parent, include the original of following component Material:100 grams of oxygenation efficiency are 20% nano oxidized cellulose slurries (solid content 12%), 30 grams of starch, 5 gram mass concentration are 30% Oxidant H2O2, 1 gram of stabilizer polyvinyl alcohol, 1 gram of preservative ammonium pentaborate and 1 gram of emulsified wax;In nano oxidized cellulose The content that nanofiber length is 1~100nm is 60%;The content that nanofiber length is 100~1000nm is 35%;Fiber Length is that 1 μm~10mm content is 10%.
The preparation method using nano oxidized cellulose slurries as the starch adhesive of parent of the present embodiment, including following step Suddenly:
(1) 10 grams of pulp boards are weighed, it is the shear agitation 2h at a temperature of 55 DEG C in 50% sulfuric acid solution to add 90 grams of concentration (shear rate 4000rpm), then add the oxidant H that 2 gram mass concentration are 30%2O2Continue shear agitation reaction 1.0h;600 grams of water terminating reactions are eventually adding, the product of acquisition is fitted into bag filter, dialyse is to pH=2, solid content 12%th, oxygenation efficiency is 20% nano oxidized cellulose slurries;Nanofiber length is distributed in the nano oxidized cellulose slurries: 1~100nm, 60%;100~1000nm, 35%;1 μm~10mm, 10%.
(2) 100 grams of nano oxidized cellulose slurries for taking step (1) to obtain, 30 grams of starch and 5 gram masses are added in batches Concentration is 30% oxidant H2O2, 2.4 grams of starch and 0.75 gram of oxidant quality are added for the first time, are sufficiently stirred at 60 DEG C Gelatinization reaction 0.5h;Second 12 grams of starch and 2.25 grams of oxidants, 0.5h is sufficiently stirred at 60 DEG C;Third time adds 15.6 Gram starch and 2 grams of oxidants, 0.5h is sufficiently stirred at 60 DEG C;It is then respectively adding 1 gram of stabilizer polyvinyl alcohol, 1 gram of anti-corrosion Agent ammonium pentaborate and 1 gram of emulsified wax, each component is stirred well at 60 DEG C and is uniformly dispersed, fully reacts, is obtained with nanometer Oxycellulose slurries are the starch adhesive of parent.
Sanding is carried out to moisture content 4.5% or so, breadth 300mm × 300mm veneers surface;Received manufactured in the present embodiment Rice oxycellulose slurries are that the starch adhesive of parent by resin added is 300g/m2Uniformly it is applied to veneer surface;Then it is pre- Precompressed 2min under press;It is again 3MPa in thermal pressure, hot pressing time carries out hot pressing under the conditions of being 1mm/min.
The glued board water resistance of above-mentioned preparation is measured by GB/T9846-2004II class glued board standards;According to GB/ T9846-2004II class glued board standards, (with reference to the sample preparation of GB/T17657-1999 standards) glued board is measured using puller system Bonding strength, as a result as shown in table 1.
Embodiment 4:
A kind of starch adhesive of the invention using nano oxidized cellulose slurries as parent, include the original of following component Material:100 grams of oxygenation efficiency are 30% nano oxidized cellulose slurries (solid content 12%), 40 grams of starch, 5 gram mass concentration are 30% Oxidant H2O2, 2 grams of stabilizer polyvinyl alcohol, 2 grams of preservative ammonium pentaborates and 2 grams of emulsified waxes;In nano oxidized cellulose The content that nanofiber length is 1~100nm is 70%;The content that nanofiber length is 100~1000nm is 20%;Fiber Length is that 1 μm~10mm content is 10%.
The preparation method using nano oxidized cellulose slurries as the starch adhesive of parent of the present embodiment, including following step Suddenly:
(1) 12 grams of pulp boards are weighed, it is the shear agitation at a temperature of 55 DEG C in 60% sulfuric acid solution to add 100 grams of concentration 3h (shear rate 5000rpm), then add the oxidant H that 2 gram mass concentration are 30%2O2Continue shear agitation reaction 1.0h;800 grams of water terminating reactions are eventually adding, the product of acquisition is fitted into bag filter, dialyse is to pH=1, solid content 12%th, oxygenation efficiency is 30% nano oxidized cellulose slurries;Nanofiber length is distributed in the nano oxidized cellulose slurries: 1~100nm, 70%;100~1000nm, 20%;1 μm~10mm, 10%.
(2) 100 grams of nano oxidized cellulose slurries for taking step (1) to obtain, 40 grams of starch and 5 gram masses are added in batches Concentration is 30% oxidant H2O2, 4 grams of starch and 0.5 gram of oxidant quality are added for the first time, and it is anti-that gelatinization is sufficiently stirred at 70 DEG C Answer 1h;Second 16 grams of starch and 2.5 grams of oxidants, 1h is sufficiently stirred at 70 DEG C;Third time adds 20 grams of starch and 2 grams of oxygen Agent, 1h is sufficiently stirred at 70 DEG C;It is then respectively adding 2 grams of stabilizer polyvinyl alcohol, 2 grams of preservative ammonium pentaborates and 2 grams Emulsified wax, each component is stirred well at 60 DEG C and is uniformly dispersed, fully reacts, obtain using nano oxidized cellulose slurries as The starch adhesive of parent.
Sanding is carried out to moisture content 4.5% or so, breadth 300mm × 300mm veneers surface;Received manufactured in the present embodiment Rice oxycellulose slurries are that the starch adhesive of parent by resin added is 300g/m2Uniformly it is applied to veneer surface;Then it is pre- Precompressed 2min under press;It is again 3MPa in thermal pressure, hot pressing time carries out hot pressing under the conditions of being 1mm/min.
The glued board water resistance of above-mentioned preparation is measured by GB/T9846-2004II class glued board standards;According to GB/ T9846-2004II class glued board standards, (with reference to the sample preparation of GB/T17657-1999 standards) glued board is measured using puller system Bonding strength, as a result as shown in table 1.
Comparative example:
The starch adhesive of this comparative example, include the raw material of following component:100 grams of distilled water, 30 grams of starch, 10 grams of dryings Nano-cellulose, 1 gram of stabilizer polyvinyl alcohol, 1 gram of preservative ammonium pentaborate and 1 gram of emulsified wax.
Its preparation process is as follows:30 grams of starch are disposably added in 100 grams of distilled water, 0.5h is sufficiently stirred at 60 DEG C, Then the nano-cellulose that addition 10g is dried, 1 gram of stabilizer polyvinyl alcohol, 1 gram of preservative ammonium pentaborate and 1 gram of emulsified wax, Each component is stirred well at 50 DEG C to be uniformly dispersed, that is, obtains starch adhesive.
Sanding is carried out to moisture content 4.5% or so, breadth 300mm × 300mm veneers surface;Prepared by this comparative example general Logical starch adhesive is 300g/m by resin added2Uniformly it is applied to veneer surface;Then precompressed 2min under preformer;Again in hot pressing Power is 3MPa, and hot pressing time carries out hot pressing under the conditions of being 1mm/min.
The glued board water resistance of above-mentioned preparation is measured by GB/T9846-2004II class glued board standards;According to GB/ T9846-2004II class glued board standards, (with reference to the sample preparation of GB/T17657-1999 standards) glued board is measured using puller system Bonding strength, as a result as shown in table 1.
The intensity and water resistance experimental result of the starch adhesive of table 1:
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Contrast experiment
Dry strength/MPa 1.85 1.90 2.62 2.32 1.01
Wet strength/MPa 0.64 0.71 0.91 0.78 0.26
As it can be seen from table 1 the present invention use nano oxidized cellulose slurries be parent starch adhesive intensity with Water resistance performance is significantly better than that the performance of the common adhesive of contrast experiment.

Claims (8)

  1. A kind of 1. starch adhesive using nano oxidized cellulose slurries as parent, it is characterised in that in parts by weight, including with The raw material of lower component:100 parts of oxygenation efficiency are 5%~30% nano oxidized cellulose slurries, 10~40 parts of starch, 2~5 parts of oxidations Agent, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax;In the nano oxidized cellulose slurries The oxycellulose mass fraction that fibre length is 1~100nm is 35%~70%;Fibre length is 100~1000nm oxygen Cellulose mass fraction is 20%~50%;The oxycellulose mass fraction that fibre length is 1 μm~10mm is 10%~ 15%.
  2. 2. starch adhesive as claimed in claim 1, it is characterised in that the solid content of the nano oxidized cellulose slurries is 8%~12%.
  3. 3. starch adhesive as claimed in claim 1, it is characterised in that the oxidant is H2O2Or/and NaClO;It is described steady It is macrogol to determine agent;The preservative is ammonium pentaborate.
  4. A kind of 4. preparation method using nano oxidized cellulose slurries as the starch adhesive of parent, it is characterised in that including with Lower step:
    (1) 8~12 parts of pulp boards are taken, are added in 80~100 parts of sulfuric acid solutions, at a temperature of 50~55 DEG C shear agitation 1~ After 3h, add 1~2 part of oxidant and continue 0.5~1.0h of shear agitation reaction;200~1000 parts of water are eventually adding to terminate instead Should, product will be obtained and dialysed to pH=1~5, the nano oxidized cellulose slurries that oxygenation efficiency is 5%~30%;
    (2) 100 parts of nano oxidized cellulose slurries for taking step (1) to obtain, 10~40 parts of starch and 2~5 parts are added in batches Oxidant, 0.1~2 part of stabilizer, 0.1~2 portion of preservative and 0.1~2 part of emulsified wax are added after being sufficiently stirred, 50 Each component is stirred well at~70 DEG C to be uniformly dispersed, that is, obtains the starch adhesive.
  5. 5. preparation method as claimed in claim 4, it is characterised in that in the step (2), add starch and oxidation in batches Agent concretely comprises the following steps:10%~15% of 5%~10% and oxidant quality of starch quality in proportioning is added for the first time, 0.5~1h of gelatinization reaction is sufficiently stirred at 50~70 DEG C;Second of 30~40% and the oxidant for adding starch quality in proportioning The 40%~50% of quality, 0.5~1h is sufficiently stirred at 50~70 DEG C;Third time add proportioning in starch quality 50%~ 65% and the 35%~50% of oxidant quality, it is sufficiently stirred 0.5~1h at 50~70 DEG C.
  6. 6. preparation method as claimed in claim 4, it is characterised in that the nano oxidized cellulose slurry that the step (1) obtains The solid content of liquid is 8%~12%;Fibre length is 1~100nm oxycellulose in the nano oxidized cellulose slurries Mass fraction is 35%~70%;The oxycellulose mass fraction that fibre length is 100~1000nm is 20%~50%;It is fine It is 10%~15% to tie up the oxycellulose mass fraction that length is 1 μm~10mm.
  7. 7. preparation method as claimed in claim 4, it is characterised in that the oxidant is H2O2Or/and NaClO;The stabilization Agent is macrogol;The preservative is ammonium pentaborate.
  8. 8. preparation method as claimed in claim 4, it is characterised in that in the step (1), the mass concentration of sulfuric acid solution is 20%~60%;Shear rate is 2000~5000rpm.
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