CN106833431B - A kind of adhesive and its preparation method and application - Google Patents
A kind of adhesive and its preparation method and application Download PDFInfo
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- CN106833431B CN106833431B CN201611228117.0A CN201611228117A CN106833431B CN 106833431 B CN106833431 B CN 106833431B CN 201611228117 A CN201611228117 A CN 201611228117A CN 106833431 B CN106833431 B CN 106833431B
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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
- C09J107/00—Adhesives based on natural rubber
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- 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
- C09J107/00—Adhesives based on natural rubber
- C09J107/02—Latex
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J115/00—Adhesives based on rubber derivatives
-
- 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
-
- 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
- C09J175/06—Polyurethanes from polyesters
Abstract
The present invention provides a kind of adhesives and its preparation method and application.A kind of adhesive mainly includes high-molecular compound, biomass graphene, water, in which: by weight, 100 parts of high-molecular compound, biomass graphene accounts for 0.2wt~10wt% of high-molecular compound, and high-molecular compound contains 30wt~70wt% admittedly；The high-molecular compound is selected from one of natural rubber, modified natural rubber, synthetic rubber, polyurethanes glue or a variety of, preferably modified natural rubber/polyurethanes glue.Adhesive of the invention solves the problems, such as that existing adhesive has a single function, and shows excellent Low Temperature Far Infrared function, bacteriostasis antibiosis function and stronger firmness.
Description
Technical field
The present invention relates to chemical technology fields, more particularly, to a kind of adhesive and its preparation method and application.
Background technique
China is shoemaking big country, and the dosage of adhesive is very huge.Rubber adhesive is configured by base-material of rubber
Adhesive, almost all of natural rubber and synthetic rubber may be used to configure adhesive, according to the composition of rubber base-material,
The agent of natural rubber gluing and synthetic rubber adhesive two major classes can be divided into.The demand of adhesives for shoes with shoemaking industry development
It is in rising trend.
The prior art is all only absorbed in the improvement of cohesive force to the exploitation of adhesive, therefore adhesive in the market only bonds
Function has a single function.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of adhesive, and the adhesive solves existing adhesive function list
One the problem of, shows excellent Low Temperature Far Infrared function, bacteriostasis antibiosis function and stronger firmness.
The second object of the present invention is to provide the preparation method of above-mentioned adhesive, the preparation method process is simple,
Mild condition is easily promoted.
The third object of the present invention is to provide the application of above-mentioned adhesive, be widely used, and can be used for footwear gluing
Agent, insole adhesive, woodenware, glued board, cement mortar, paper, cloth, leather etc. cohere.
In order to achieve the goal above, the present invention provides following technical schemes:
A kind of adhesive mainly includes high-molecular compound, biomass graphene, water, in which: by weight, macromolecule
100 parts of compound, biomass graphene accounts for 0.2wt~10wt% of high-molecular compound, high-molecular compound contain admittedly 30wt~
70wt%；
The high-molecular compound is selected from one of natural rubber, modified natural rubber, synthetic rubber, polyurethanes glue
Or a variety of, preferred modified natural rubber/polyurethanes glue.
Compared with prior art, the main distinction of the invention is to introduce biomass graphene, makes itself and macromolecule chemical combination
Object forms that bond properties is good and the adhesive of cohesive force enhancing by cross-linking reaction, and increase Low Temperature Far Infrared function and
Bacteriostasis antibiosis function.Therefore, the adhesive scope of application of the invention is wider, can be not only used for shoemaking, promotes human body from foot
Blood microcirculation plays good health-care efficacy, and can be used for other dress ornament fields and other industrial circles.
Biomass graphene of the present invention is different from graphene, the hexatomic ring honeycomb lamella with 1-10 layers of carbon
Structure；It is made using biomass as raw material, since raw material is from plant, plant itself needs to absorb mineral member from soil
Element, these mineral elements obtained during preparing biomass graphene selectivity reservation, mineral element be at least Fe,
Si, Al can also contain one or more of K, Na, Ca, Mg, P, Mn and Co.It, which is mainly prepared by the following method, (can also adopt
It is prepared with the preparation method of biomass graphene in the prior art, it can also be using the biomass graphite of Jinan holy well group production
Alkene):
First prepare cellulose:
(1) dense for the formic acid of 80wt% and the organic acid solution pair of acetic acid using total acid by after wheat straw comminution pretreatment
Treated, and wheat straw carries out boiling, and the mass ratio of acetic acid and formic acid is 1:12 in the organic acid solution of the present embodiment, and is being added
Hydrogen peroxide (the H for accounting for wheat straw raw material 1wt% is added before entering raw material2O2) it is used as catalyst, 120 DEG C of reaction temperature are controlled, instead
30min, solid-liquid mass ratio 1:10 are answered, and obtained reaction solution is subjected to first time separation of solid and liquid；
(2) being separated by solid-liquid separation obtained solid for the first time, that total acid is added is dense for the formic acid of 75wt% and the organic acid solution of acetic acid
Acid elution is carried out, wherein joined the peroxide for accounting for wheat straw raw material 8wt% in the dense organic acid solution for 75wt% of above-mentioned total acid
Change hydrogen (H2O2) it is used as catalyst, and the mass ratio of acetic acid and formic acid is 1:12, controlled at 90 DEG C, wash time 1h, solid-liquid
Mass ratio is 1:9, and reaction solution is carried out second and is separated by solid-liquid separation；
(3) it collects for the first time and is separated by solid-liquid separation obtained liquid for the second time, high temperature and pressure is carried out under 120 DEG C, 301kPa
Obtained formic acid and acetic acid vapor are condensed back into the reaction kettle of step (1) as cooking liquor, use until being evaporated by evaporation
Boiling in step (1)；
(4) it collects and is separated by solid-liquid separation obtained solid for the second time, and washed, control washing temperature is 80 DEG C, washing slurry
Concentration is 6wt%, and obtained washing slurry is carried out third time separation of solid and liquid；
(5) it collects and is separated by solid-liquid separation obtained liquid for the third time, carry out water, sour rectifying, obtained mix acid liquor is back to step
Suddenly the boiling of step (1) is used in the reaction kettle of (1) as cooking liquor, obtained water to be back to step (5) and water is washed with water；
(6) it collects and is separated by solid-liquid separation obtained solid for the third time and is screened to obtain required screened stock cellulose.
Then graphene is prepared as raw material using the cellulose being prepared as above:
(1) under the effect of the catalyst, biomass carbon source is subjected to catalytic treatment, obtains presoma；
(2) it under conditions of protective gas, by the presoma in 140 DEG C~180 DEG C heat preservation 1.5h~2.5h, obtains
First intermediate；
(3) under conditions of protective gas, first intermediate is warming up to 350 DEG C~450 DEG C heat preservation 3h~4h,
Obtain the second intermediate；
(4) under conditions of protective gas, by second intermediate be warming up to 1100 DEG C~1300 DEG C heat preservation 2h~
4h obtains third intermediate；
(5) by the third intermediate successively alkali cleaning, pickling, washing, compound is obtained；
Heating rate in the step (3), (4) is 14 DEG C/min~18 DEG C/min.
Bonding substrates of the present invention have referred to the basic component of cementation.
Adhesive described above can also be further improved, such as:
Preferably, biomass graphene accounts for 1.5wt~5wt% of high-molecular compound, such as 2wt%, 2.5wt%,
3wt%, 3.5wt%, 4wt% etc..
Preferably, the modified natural rubber is selected from the natural rubber of olefin(e) acid graft modification；The olefin(e) acid is preferably selected from first
One of base acrylic acid, acrylic acid, maleic acid are a variety of, more preferable methacrylic acid.
Natural rubber is modified by olefin(e) acid, and adhesion strength and stability improve, and the crosslinking with biomass graphene
Effect enhancing, amalgamation is higher, is conducive to the far infrared, bacteria resistance function and the mechanical property that improve adhesive.Preferably, described
The accounting of olefin(e) acid section described in the natural rubber of olefin(e) acid graft modification is 2-10wt%.
Preferably, the biomass graphene is homogenization processing, it may be assumed that D90 norm controlling is at 100 μm hereinafter, D10 refers to
Mark control is at 20 μm or less；D90 norm controlling at 20 times of D10 index hereinafter, it is preferred that 10 times hereinafter, more preferably 5 times or less；
Preferably, function dough is carried out to the biomass graphene to be modified；
Preferably, functional group's metaplasia substance graphene includes any one being grafted in hydroxyl, carboxyl or amino
Or the biomass graphene of a variety of functional groups；The above modified biomass graphene is connected with the high function assessment group of more activity,
Not only it had been conducive to the crosslinking with bonding substrates, but also has been conducive to improve the cohesive force of adhesive, while dispersion degree is more preferable in water, therefore performance
It is more stable.
Preferably, biomass graphene carboxylated method of modifying includes: by biomass graphene in TEMPO oxidized catalyst precursor
Under the action of system, catalytic oxidation is carried out, until the pH of reaction system is constant or alcohols material termination reaction is added, washing is dry
It is dry to obtain the final product；
Preferably, the catalytic oxidation pH control between 2-13, between preferably 3.5-6 or 9.5-11.5 it
Between；
Preferably, TEMPO catalytic oxidation system includes containing TEMPO and/or its derivative, sodium hypochlorite, sodium bromide
Water solution system；More preferably containing TEMPO, sodium hypochlorite, sodium bromide water solution system；The pH of the catalytic oxidation
Preferably 10-11；
Preferably, the TEMPO derivative is selected from 2-aza-adamantane-N- oxygroup, 1- methyl -2-aza-adamantane-N-
One of oxygroup, 1,3- dimethyl -2-aza-adamantane-N- oxygroup, 4- hydroxyl TEMPO derivative are a variety of；
Preferably, the additional amount of TEMPO and/or its derivative is the 0.05%~5% of the biomass graphene weight,
It is preferred that 0.1%~3%, further preferably 0.3%~2%, more preferable 0.5%-1%；Specific additional amount can be 0.1%,
0.3%, 0.8%, 1%, 1.2%, 1.5%, 2.5%, 3.5%, 4%, 4.5% etc.；
Preferably, the additional amount of sodium hypochlorite is the 10%~500% of the biomass graphene weight, preferably 30%~
95%, further preferably 40%-75%, the specific can be that 50%, 70%, 100%, 120%, 135%, 160%, 200%,
300%, 400%, 450% etc..
Preferably, the additional amount of sodium bromide is the 0.5%~50% of the biomass graphene weight, preferably 10%~
30, further preferably 3%~20%, more preferable 5%~10%, the specific can be that 3%, 8%, 10%, 12%, 15%, 18%,
25%, 35%, 45% etc..
Specific steps are as follows:
It is made into aqueous solution by TEMPO and/or its derivative and with NaBr, stirring and dissolving is complete, obtains mixed liquor, is then added
Biomass graphene continues to stir, and then adds the 10-30% of liquor natrii hypochloritis's total amount, is stirred to react, residue 70% by
It is gradually added, after reaction, removal solvent obtains modified biomass graphene powder.
Preferably, the modifying agent is surfactant, and the surfactant is preferably selected from anionic surfactant,
More preferable neopelex；The additional amount of surfactant be bonding substrates 1~2wt%, more preferable 1.5~
2wt%.On the one hand surfactant can promote the dispersion degree of adhesive in water, be on the one hand conducive to the bonding of enhancing adhesive
Strength and stability.
The solid content of the adhesive is 35wt%~60wt%, preferably 40wt%~50wt%.
It further include nano-cellulose in the adhesive, the content of the nano-cellulose is biomass graphene
2wt% is hereinafter, it is preferred that 0.3-1.5wt%；The diameter of the nano-cellulose is 20nm hereinafter, it is preferred that 10nm is hereinafter, further preferably
2-5nm, the specific can be that 15nm, 12nm, 8nm, 5nm, 3nm etc.；The draw ratio of the nano-cellulose is 100 or more, excellent
200-800 is selected, further preferably 500-800, the specific can be that 150,280,360,420,580,640,710,780,1000 etc..
The preparation method of the modified adhesive of biomass graphene described above, which comprises the following steps:
By biomass graphene and high-molecular compound at 80~120 DEG C hybrid reaction, selective addition suitable quantity of water and appropriate table
Face activating agent mixes, and the reaction was continued at 90~120 DEG C, consolidates high-molecular compound and contains for 30-70wt%.
Be also possible to biomass graphene dispersion Yu Shuizhong obtaining biomass graphene dispersing solution, then with macromolecule
Compound hybrid reaction at 80~120 DEG C adds surfactant and mixes, and more preferable 90~120 DEG C of hybrid reaction temperature；
It is introduced that is, biomass graphene can be seperated form, the form for being also possible to dispersion liquid introduces；Only
The water content in biomass graphene aqueous solution is wanted to guarantee that the high-molecular compound of the adhesive finally obtained is contained in 30- admittedly
70wt%.
Preferably, when the high-molecular compound is polyurethanes glue, the method for the hybrid reaction is in following manner
One kind:
The method of biomass graphene modified polyurethane glue includes:
Mode one mixes polyisocyanates with biomass graphene, then with polyethers or polyester polyol hybrid reaction；
Mode two mixes polyether/polyester polyol with biomass graphene, then with polyisocyanates hybrid reaction；
Mode three, by part polyisocyanates, polyether/polyester polyol and biomass graphene hybrid reaction, then with it is surplus
Remaining polyisocyanates hybrid reaction.
Preferably, the high-molecular compound is the natural rubber of methacrylic acid graft modification, preparation method are as follows: will
In natural rubber dissolution solvent, methacrylic acid and initiator is added, under the conditions of 60~90 DEG C, stirs 4~5 hours, stops
Heating, cooling reaction system to room temperature, polymerization inhibitor is added, and reaction was completed, then purifies；The preferred benzoyl peroxide first of initiator
Acyl, the polymerization inhibitor are preferably hydroquinone.
Wherein, high-molecular compound can be mixed directly for the form of adhesive finished product with biomass graphene, can also be with
Its basic material is taken to mix with biomass graphene.
During preparing adhesive, nano-cellulose can also be added, the content of the nano-cellulose is biology
The 2wt% of matter graphene is hereinafter, it is preferred that 0.3-1.5wt%；
Preferably, before biomass graphene is mixed with high-molecular compound, first by biomass graphene dispersion to water
And/or in ethanol solution, dispersion liquid is obtained, nano-cellulose mixing is added, removes solvent, obtain containing nanofiber
The biomass graphene of element；
It is also possible to before biomass graphene mixes with high-molecular compound, first by biomass graphene dispersion to water
In solution, add nano-cellulose mixing, obtain the biomass graphene dispersing solution containing nano-cellulose, then with
High-molecular compound hybrid reaction at 80~120 DEG C adds surfactant and mixes, and hybrid reaction temperature more preferable 90~
120℃；
Preferably, the concentration of biomass graphene is 10-200mg/g, preferably 20-100mg/g in the dispersion liquid, then excellent
Select 30-50mg/g.
Preferably, it is ultrasound, time 10-200min that mode, which is mixed,.
The application of the adhesive can be used for footwear adhesive, insole adhesive, woodenware, glued board, cement bonded sand
Slurry, paper, cloth, leather etc. cohere.
To sum up, compared with prior art, the present invention achieves following technical effect:
(1) by introducing biomass graphene into existing adhesive, far infrared and bacteria resistance function is increased, is improved simultaneously
The firmness of adhesive.
(2) a kind of excellent modified biomass graphene product is provided, more preferably with the degrees of cross linking of bonding substrates, for into one
Step improves far infrared, bacteria resistance function and adhesive property and provides new opportunity.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Biomass graphene used in Examples below is all made of following methods and is made:
Biomass graphene A: preparation method is that China Patent Publication No. is CN105502330A embodiment 4, and D90 is
20um, D10 4um.
Biomass graphene B: preparation method is that China Patent Publication No. is CN104016341A embodiment 7, and D90 is
50um, D10 7um.
Biomass graphene C: preparation method is that China Patent Publication No. is CN104724699A embodiment 1, and D90 is
10um, D10 3um.
The biomass graphene of carboxylated the preparation method is as follows:
By 100mg biomass graphene ultrasonic disperse in 100ml water, the biomass graphene for obtaining 1mg/ml is water-soluble
Then 6g sodium hydroxide and 5g bromoacetic acid ultrasound 3h is added in liquid, so that the epoxy group of biomass graphene surface and hydroxyl conversion
It for carboxyl, filters while hot, removes impurity, 65 DEG C of vacuum drying obtain carboxylated biomass graphene again later.
Alternatively,
By biomass graphene under the action of TEMPO catalytic oxidation system, catalytic oxidation is carried out, until reactant
The pH of system is constant or alcohols material termination reaction is added, and washing is drying to obtain；
Preferably, the catalytic oxidation pH control between 2-13, between preferably 3.5-6 or 9.5-11.5 it
Between.
TEMPO catalytic oxidation system include containing TEMPO and/or its derivative, sodium hypochlorite, sodium bromide aqueous liquid
System；More preferably containing TEMPO, sodium hypochlorite, sodium bromide water solution system；The pH of the catalytic oxidation is preferably
10-11；
Preferably, the TEMPO derivative is selected from 2-aza-adamantane-N- oxygroup, 1- methyl -2-aza-adamantane-N-
One of oxygroup, 1,3- dimethyl -2-aza-adamantane-N- oxygroup, 4- hydroxyl TEMPO derivative are a variety of；
Preferably, the additional amount of TEMPO and/or its derivative is the 0.05%~5% of the biomass graphene weight,
It is preferred that 0.1%~3%, further preferably 0.3%~2%, more preferable 0.5%-1%；
Preferably, the additional amount of sodium hypochlorite is the 10%~500% of the biomass graphene weight, preferably 30%~
95%, further preferably 40%-75%；
Preferably, the additional amount of sodium bromide is the 0.5%~50% of the biomass graphene weight, preferably 10%~
30, further preferably 3%~20%, more preferable 5%~10%.
The size controlling of biomass graphene: D90 norm controlling is at 100 μm hereinafter, D10 norm controlling is at 20 μm or less；
10 times in D10 index of D90 norm controlling.
Illustratively, polyurethane adhesive prepare it is as follows:
The pure and mild isophorone diisocyanate of a certain proportion of polyester binary is mixed, is added under 60-80 DEG C of nitrogen protection
Enter dibutyl tin dilaurate initiated polymerization；Changed according to system viscosity, acetone is added in due course and guarantees that reaction is normally carried out；
2,2- dihydromethyl propionic acid and trimethylolpropane are added later, and the reaction was continued, adds triethylamine neutralization reaction；It, will after cooling
2,4- diamino benzene sulfonic acid sodium water solutions are gradually added dropwise, and carry out chain extending reaction；Then distilled water and EVA are added, and in high speed
Stir emulsified, the acetone in last removed under reduced pressure system is to get Aqueous Polyurethane Adhesives.
Specifically, such as preparation example 1:
The pure and mild 20 parts of isophorone diisocyanate of 80 parts of polyester binaries are mixed, are added dropwise 0.3 under 75 DEG C of nitrogen protections
Part dibutyl tin dilaurate reacts 2h；100 parts of acetone are added；1.6 parts of 2,2- dihydromethyl propionic acids and 1.5 part three are added later
Hydroxymethyl-propane reacts 1.5h, adds 0.5 part of triethylamine neutralization reaction 30min；30 DEG C are cooled to, concentration, which is gradually added dropwise, is
5 parts of reaction 30min of 2,4- diamino benzene sulfonic acid sodium water solution of 5wt%；Then water and 20 parts of EVA are added, and in high-speed stirring
Emulsified 30min is mixed, the acetone in last removed under reduced pressure system is to get Aqueous Polyurethane Adhesives.
Embodiment 1
By weight, 100 parts of natural rubber are taken, A5 parts of biomass graphene, the two is mixed, and mix and stir at 120 DEG C
Mix 2 hours, water be added later, 2 parts of neopelex mixes, make natural rubber consolidate containing control 50wt% to get
Adhesive.
Embodiment 2-5
It is only that the dosage of biomass graphene A is respectively 0.2 part and natural rubber contains admittedly and is with the difference of embodiment 1
It is 40wt% that 70wt%, 2 parts and natural rubber, which contain admittedly and contain admittedly for 60wt%, 8 parts and natural rubber, 10 parts and natural rubber contain admittedly
For 30wt%.
Embodiment 6-7
Difference with embodiment 1, which is only that, replaces with biomass graphene B, biomass graphene for biomass graphene A
C。
Embodiment 8
It is with the distinctive points of embodiment 1, biomass graphene is replaced with into modified biomass graphene, specific modified step
Suddenly are as follows:
(1) 1 part of biomass graphene A is taken, 200 parts of water are added and stir to form uniform slurries, then adds TEMPO and urges
Change oxidising composition (0.01 part of TEMPO, 1 part of sodium hypochlorite, 0.05 part of sodium bromide) to be stirred to react, passes through the hydrogen-oxygen of 0.5wt%
The glacial acetic acid solution adjusting for changing sodium solution and 1wt% is maintained at the pH of reaction system within the scope of 10.5-11, when pH no longer changes
Stop reaction afterwards and obtains suspension, reaction time 2.5h.
(2) suspension for obtaining step (1) filters, and is repeatedly washed, is centrifuged with water, and each centrifugal speed is
1000rpm, each centrifugation time are 5min, and the pH of final washing to suspension is neutrality, obtain modified biomass stone after dry
Black alkene A powder.
Embodiment 9
It is with the distinctive points of embodiment 8,5 parts of modified biomass graphene A powders is added in 100 parts of water and are divided
Then dispersion liquid is then added in 100 parts of natural emulsions, the two is mixed, and be mixed 2 hours at 120 DEG C, is being added 1
Part neopelex mixes, and control natural emulsion contains 40wt% admittedly up to adhesive.
Embodiment 10
Difference with embodiment 8 is that TEMPO catalysis oxidation composition each component content is not in modification procedure (1) step
Together, specifically: 0.005gTEMPO, 0.75g sodium hypochlorite, 0.1g sodium bromide.
Embodiment 11
Difference with embodiment 8 is that TEMPO catalysis oxidation composition each component content is not in modification procedure (1) step
Together, specifically: 0.05gTEMPO, 5g sodium hypochlorite, 0.2g sodium bromide.
Embodiment 12
Difference with embodiment 1 is only that it is 10nm that 0.025 part of diameter is added in biomass graphene A, and draw ratio is
200 nano-cellulose.
Embodiment 13
Difference with embodiment 1 is only that it is 5nm that 0.05 part of diameter is added in biomass graphene A, and draw ratio is
500 nano-cellulose.
Embodiment 14
Difference with embodiment 1 is only that it is 3nm, draw ratio 800 that 0.1 part of diameter is added in biomass graphene A
Nano-cellulose.
Embodiment 15
5 parts of biomass graphene A are added in 100 parts of water-borne polyurethane bonds that preparation example 1 obtains, are uniformly mixed, control
Polyurethane processed contains 50wt% admittedly.
Embodiment 16
It is with the distinctive points of embodiment 15, the addition opportunity of 5 parts of biomass graphene A is in preparation example 1 first by 5 parts
Biomass graphene A mixes dispersion with 80 parts of polyester diols.
Embodiment 17
It is with the distinctive points of embodiment 15, the addition opportunity of 5 parts of biomass graphene A is in preparation example 1 first by 5 parts
Biomass graphene A mixes dispersion with 20 parts of isophorone diisocyanate.
Embodiment 18
It is with the distinctive points of embodiment 15, the addition opportunity of 5 parts of biomass graphene A is in preparation example first by 5 parts
Biomass graphene A mixes dispersion with 60 parts of polyester diols, 20 parts of isophorone diisocyanate mixing is added, at 75 DEG C
It is added dropwise in 0.3 part of dibutyl tin dilaurate reaction process under nitrogen protection, adds remaining 20 parts of polyester diols.
Embodiment 19
The difference from embodiment 1 is that natural rubber is replaced with modified natural rubber.
Modified natural rubber the preparation method is as follows:
The natural rubber of 100g is dissolved in the water of 500g and the in the mixed solvent of whey, the methacrylic acid of 20g is added,
It stirs evenly.The benzoyl peroxide of 2~5g is added, under the conditions of 60~90 DEG C, stirs 4~5 hours, stops heating, it is cooling
Reaction system is to room temperature；1g hydroquinone is added.Extraction and separation go out copolymer mixture solution to get modified natural rubber.
Comparative example 1 is preparation example 1.
Application examples
Insole is made using the adhesive of above-described embodiment 1-19 preparation, the specific steps are as follows:
EVA foam is chosen as substrate, above-mentioned adhesive is uniformly applied to substrate surface, insole fabric is equal
Even to be covered on substrate surface, hot pressing 3min, is placed at room temperature for and can be prepared by test insole for 24 hours under a certain pressure.
Test heating rate, deodorant function, the mechanical property of above application examples product.
Heating rate test method: at 17 DEG C of room temperature；Under the conditions of humidity 85%, using model PHLIPS infrared lamp away from
From application examples product is irradiated at height of table top 51cm, data are recorded, the following table 1 is specifically shown in.
Deodorant function detection: the adult male of 19 foot odours is chosen, 1 embodiment of every Member Authentication, verification method is such as
Under: such as verifying embodiment 1, then member dresses insole prepared by embodiment 1 and insole prepared by comparative example 1 is padded respectively in left and right
In the shoes of foot, detect whether to foul after a week.
Experiment of machanics:
1. cutting sample with cut-off knife；
2. pushing insole and fabric aside 3cm；
3. every 2cm takes a point since at the 3cm pushed aside, 5 mark points are continuously taken；
4. starting peeling strength test machine, its speed is set as 50mm/min, the two sides that sample has been pushed aside is pressed from both sides respectively
On the fixture up and down of puller system.
5. starting peeling strength test machine feeler switch, testing machine starts to test, the 3cm pushed aside be in first mark point it
Between distance do not have to reading；
6. since first mark point, the minimum value between every two mark point is read, available 4 minimum values,
Then the minimum value of acquisition is averaged, then divided by the width of sample, then obtains the peel strength of sample.
As a result such as the following table 1 to 3.
1 temperature rise data of table
2 deodorant function detection data of table
3 mechanical property of table
| Sample | Width | Pulling force (N) |
| Embodiment 1 | 10mm | 10.7 |
| Embodiment 2 | 10mm | 9.7 |
| Embodiment 3 | 10mm | 10.5 |
| Embodiment 4 | 10mm | 10.3 |
| Embodiment 5 | 10mm | 10.1 |
| Embodiment 6 | 10mm | 10.4 |
| Embodiment 7 | 10mm | 10.5 |
| Embodiment 8 | 10mm | 10.9 |
| Embodiment 9 | 10mm | 10.8 |
| Embodiment 10 | 10mm | 10.9 |
| Embodiment 11 | 10mm | 11.1 |
| Embodiment 12 | 10mm | 11.4 |
| Embodiment 13 | 10mm | 11.6 |
| Embodiment 14 | 10mm | 11.9 |
| Embodiment 15 | 10mm | 10.4 |
| Embodiment 16 | 10mm | 10.5 |
| Embodiment 17 | 10mm | 10.7 |
| Embodiment 18 | 10mm | 10.9 |
| Embodiment 19 | 10mm | 10.3 |
| Comparative example | 10mm | 9.1 |
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (54)
1. a kind of adhesive, which is characterized in that mainly include high-molecular compound, biomass graphene, water, in which: by weight
Meter, 100 parts of high-molecular compound, biomass graphene accounts for 0.2wt ~ 10wt% of high-molecular compound, and high-molecular compound contains admittedly
30wt~70wt%；
The high-molecular compound is selected from one of natural rubber, modified natural rubber, synthetic rubber or a variety of；
The biomass graphene partial size are as follows: D90 norm controlling is at 100 μm hereinafter, D10 norm controlling is at 20 μm or less；D90 refers to
Mark 20 times or less controlled in D10 index.
2. adhesive according to claim 1, which is characterized in that the high-molecular compound is polyurethanes glue.
3. adhesive according to claim 1, which is characterized in that
It further include nano-cellulose, the content of the nano-cellulose is the 2wt% or less of biomass graphene.
4. adhesive according to claim 3, which is characterized in that the content of the nano-cellulose is biomass graphene
0.3wt ~ 1.5wt%.
5. adhesive according to claim 1, which is characterized in that the high-molecular compound is modified natural rubber/poly-
Urethane class glue.
6. adhesive according to claim 1, which is characterized in that biomass graphene account for the 1.5wt of high-molecular compound ~
5wt%。
7. adhesive according to claim 5, which is characterized in that the modified natural rubber is selected from olefin(e) acid graft modification
Natural rubber.
8. adhesive according to claim 7, which is characterized in that the olefin(e) acid is selected from methacrylic acid, acrylic acid, along fourth
One of enedioic acid is a variety of.
9. adhesive according to claim 7, which is characterized in that the olefin(e) acid is methacrylic acid.
10. adhesive according to claim 7, which is characterized in that described in the natural rubber of the olefin(e) acid graft modification
The accounting of olefin(e) acid section is 2wt ~ 10wt%.
11. adhesive according to claim 1, which is characterized in that the biomass graphene partial size are as follows: D90 index control
Make 10 times or less in D10 index.
12. adhesive according to claim 1, which is characterized in that the biomass graphene partial size are as follows: D90 index control
Make 5 times or less in D10 index.
13. adhesive according to claim 1, which is characterized in that be modified processing to the biomass graphene, have
Body is functional group's metaplasia substance graphene.
14. adhesive according to claim 13, which is characterized in that functional group's metaplasia substance graphene includes grafting
There is the biomass graphene of any one or more functional group in hydroxyl, carboxyl or amino.
15. adhesive according to claim 14, which is characterized in that biomass graphene carboxylated method of modifying includes:
By biomass graphene under the action of TEMPO catalytic oxidation system, catalytic oxidation is carried out, until the pH of reaction system is permanent
Fixed or addition alcohols material terminates reaction, and washing is drying to obtain.
16. adhesive according to claim 15, which is characterized in that the pH of catalytic oxidation control 2-13 it
Between.
17. adhesive according to claim 15, which is characterized in that the pH of the catalytic oxidation is controlled in 3.5-6
Between or 9.5-11.5 between.
18. adhesive according to claim 15, which is characterized in that TEMPO catalytic oxidation system includes containing TEMPO
And/or the water solution system of its derivative, sodium hypochlorite, sodium bromide.
19. adhesive according to claim 15, which is characterized in that TEMPO catalytic oxidation system is to contain TEMPO, secondary
The water solution system of sodium chlorate, sodium bromide.
20. adhesive according to claim 15, which is characterized in that the pH of the catalytic oxidation is 10-11.
21. adhesive according to claim 18, which is characterized in that the TEMPO derivative is selected from 2-aza-adamantane-
N- oxygroup, 1- methyl -2-aza-adamantane-N- oxygroup, 1,3- dimethyl -2-aza-adamantane-N- oxygroup, 4- hydroxyl TEMPO
One of derivative is a variety of.
22. adhesive according to claim 18, which is characterized in that the additional amount of TEMPO and/or its derivative is described
The 0.05%~5% of biomass graphene weight.
23. adhesive according to claim 18, which is characterized in that the additional amount of TEMPO and/or its derivative is described
The 0.1%~3% of biomass graphene weight.
24. adhesive according to claim 18, which is characterized in that the additional amount of TEMPO and/or its derivative is described
The 0.3%~2% of biomass graphene weight.
25. adhesive according to claim 18, which is characterized in that the additional amount of TEMPO and/or its derivative is described
The 0.5%-1% of biomass graphene weight.
26. adhesive according to claim 19, which is characterized in that the additional amount of sodium hypochlorite is the biomass graphite
The 10%~500% of alkene weight.
27. adhesive according to claim 19, which is characterized in that the additional amount of sodium hypochlorite is the biomass graphite
The 30%~95% of alkene weight.
28. adhesive according to claim 19, which is characterized in that the additional amount of sodium hypochlorite is the biomass graphite
The 40%-75% of alkene weight.
29. adhesive according to claim 19, which is characterized in that the additional amount of sodium bromide is the biomass graphene
The 0.5%~50% of weight.
30. adhesive according to claim 19, which is characterized in that the additional amount of sodium bromide is the biomass graphene
The 10%~30% of weight.
31. adhesive according to claim 19, which is characterized in that the additional amount of sodium bromide is the biomass graphene
The 3%~20% of weight.
32. adhesive according to claim 19, which is characterized in that the additional amount of sodium bromide is the biomass graphene
The 5%~10% of weight.
33. adhesive according to claim 1, which is characterized in that further include surfactant.
34. adhesive according to claim 33, which is characterized in that the surfactant is selected from anion surface active
Agent.
35. adhesive according to claim 33, which is characterized in that the surfactant is dodecyl benzene sulfonic acid
Sodium.
36. adhesive according to claim 33, which is characterized in that the additional amount of surfactant is high-molecular compound
1 ~ 2wt%.
37. adhesive according to claim 33, which is characterized in that the additional amount of surfactant is high-molecular compound
1.5 ~ 2wt%.
38. adhesive according to claim 1, which is characterized in that the solid content of high-molecular compound in the adhesive
For 35wt% ~ 60wt%.
39. adhesive according to claim 1, which is characterized in that the solid content of high-molecular compound in the adhesive
For 40wt% ~ 50wt%.
40. the preparation method of any one of the claim 1-37 adhesive, which comprises the following steps: will be biological
Matter graphene and the high-molecular compound hybrid reaction at 80 ~ 120 DEG C, selective addition suitable quantity of water mix, and make producing high-molecular
Object is closed to contain admittedly for 30-70wt%；Surfactant is additionally added when containing surfactant in the addition suitable quantity of water.
41. the preparation method of adhesive according to claim 40, which is characterized in that
When the high-molecular compound is polyurethanes glue, the method for the hybrid reaction is one of following manner:
Mode one mixes polyisocyanates with biomass graphene, then with polyethers or polyester polyol hybrid reaction；
Mode two mixes polyether/polyester polyol with biomass graphene, then with polyisocyanates hybrid reaction；
Mode three, by part polyisocyanates, polyether/polyester polyol and biomass graphene hybrid reaction, then it is more with residue
Isocyanates hybrid reaction.
42. the preparation method of adhesive according to claim 40, which is characterized in that
The high-molecular compound is the natural rubber of methacrylic acid graft modification, preparation method are as follows: natural rubber is molten
It solves in solvent, methacrylic acid and initiator is added, under the conditions of 60~90 DEG C, stir 4~5 hours, stop heating, it is cooling anti-
Answer system to room temperature, polymerization inhibitor is added, and reaction was completed, then purifies.
43. the preparation method of adhesive according to claim 40, which is characterized in that
The initiator benzoyl peroxide.
44. the preparation method of adhesive according to claim 40, which is characterized in that
The polymerization inhibitor is hydroquinone.
45. the preparation method of adhesive according to claim 40, which is characterized in that
The raw material of the adhesive further includes nano-cellulose, and the content of the nano-cellulose is the 2wt% of biomass graphene
Below.
46. the preparation method of adhesive according to claim 40, which is characterized in that
The raw material of the adhesive further includes nano-cellulose, and the content of the nano-cellulose is the 0.3- of biomass graphene
1.5wt%。
47. the preparation method of adhesive according to claim 45, which is characterized in that
It is first that biomass graphene dispersion to water and/or ethyl alcohol is molten before biomass graphene is mixed with high-molecular compound
In liquid, dispersion liquid is obtained, nano-cellulose mixing is added, removes solvent, obtain the biomass containing nano-cellulose
Graphene.
48. the preparation method of adhesive according to claim 47, which is characterized in that biomass graphite in the dispersion liquid
The concentration of alkene is 10-200mg/g.
49. the preparation method of adhesive according to claim 47, which is characterized in that biomass graphite in the dispersion liquid
The concentration of alkene is 20-100mg/g.
50. the preparation method of adhesive according to claim 47, which is characterized in that biomass graphite in the dispersion liquid
The concentration of alkene is 30-50mg/g.
51. the preparation method of adhesive according to claim 47, which is characterized in that the mode that is mixed is ultrasound, when
Between be 10-200min.
52. the application of the described in any item adhesives of claim 1-39 can be used for footwear adhesive, insole adhesive, wood
Device, cement mortar, paper, cloth, leather cohere.
53. application according to claim 52, which is characterized in that as insole adhesive.
54. application according to claim 52, which is characterized in that be used for glued board.
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| CN114288088B (en) * | 2021-12-27 | 2022-08-09 | 杭州高斯博医疗用品有限公司 | Self-dissolving strong self-adhesive elastic bandage and preparation method thereof |
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| CN105111964A (en) * | 2015-04-29 | 2015-12-02 | 宁波职业技术学院 | Graphene-modified glue |
| CN105504199A (en) * | 2015-11-27 | 2016-04-20 | 济南圣泉集团股份有限公司 | Composite polyurethane foam containing graphene, and preparation method and application thereof |
| CN106117767A (en) * | 2016-06-30 | 2016-11-16 | 济南圣泉集团股份有限公司 | A kind of method of doped graphene in the substrate |
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| CN105111964A (en) * | 2015-04-29 | 2015-12-02 | 宁波职业技术学院 | Graphene-modified glue |
| CN105504199A (en) * | 2015-11-27 | 2016-04-20 | 济南圣泉集团股份有限公司 | Composite polyurethane foam containing graphene, and preparation method and application thereof |
| CN106117767A (en) * | 2016-06-30 | 2016-11-16 | 济南圣泉集团股份有限公司 | A kind of method of doped graphene in the substrate |
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