CN109266287A - A kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance - Google Patents
A kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance Download PDFInfo
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- CN109266287A CN109266287A CN201811078546.3A CN201811078546A CN109266287A CN 109266287 A CN109266287 A CN 109266287A CN 201811078546 A CN201811078546 A CN 201811078546A CN 109266287 A CN109266287 A CN 109266287A
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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
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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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
- C08G18/6484—Polysaccharides 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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
Abstract
The present invention relates to a kind of preparation methods of hydrophobic adhesive of high heat resistance acid and alkali-resistance, belong to adhesive preparation technical field.The present invention obtains desciccate by raw material of corn stover, then desciccate is mixed with sodium stearate solution, modified filter residue is obtained by filtration, finally modified filter residue is mixed with polyvinyl alcohol water solution and other auxiliary agents, it discharges up to the hydrophobic adhesive of high heat resistance acid and alkali-resistance, increase the hydroxyl group quantity in adhesive, the cementitiousness of adhesive is set to be strengthened, by tetraethyl orthosilicate and the plant fiber being decomposed, the organic matters blended cross linking such as lignin and cellulose, the chemical stability for being conducive to the macromolecular of polycondensation generation effectively improves, to make the acid-proof alkaline of adhesive be improved, the present invention carries out surface-active modification to adhesive using odium stearate surfactant, the hydrophobicity for being conducive to adhesive is improved, it has a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrophobic adhesive of high heat resistance acid and alkali-resistance, belong to adhesive technology of preparing neck
Domain.
Background technique
Of the same race or two or more homogeneities or heterogeneous product or material can be connected by Interface Adhesion with the effects of cohesion
Together, there is the organic or inorganic of sufficient intensity, a natural or synthetic substance is referred to as adhesive after solidification.Adhesive
Have the advantages that interface infiltration and adhesion property is excellent, stress publication is continuous, light, sealing technology temperature is low etc., in building, wraps
The every field of the national economy such as dress, electronics, health care and light textile is widely used.It is glued with welding, machinery even
It connects and is known as contemporary three big interconnection techniques.
The common adhesive in China mainly has Lauxite, phenolic resin, melamine resin class adhesive at present
Deng, these synthetic adhesives molecular structure can preparatory careful design by regulating and controlling feature functionality unit gluing not only can be improved
The bond strength of agent can also assign its anti-corrosion and certain specific functions such as anti-aging.But it depends on petroleum, natural gas etc.
Non-renewable resources, and the release of the pernicious gases such as free formaldehyde, phenol is had in preparation and use process, harmful to human is strong
Health also pollutes environment.
Starch is a kind of from a wealth of sources, renewable, biodegradable natural macromolecular material, is had nontoxic, pollution-free
The features such as.If be applied on adhesive with Starch Fraction or whole high molecular materials for replacing fossil resources synthesis, it will
Great facilitation is played to adhesive industry and starch industry.However, its structure is single, cohesive force is lower, stable storing
Poor, limitation of the raw material sources vulnerable to natural conditions such as season, weather and areas of property.Therefore, them are limited to a certain extent
Use.
It, can only be simple although most of adhesive production at present on the market is simple, price is cheap but in the presence of having a single function
Conduct decoration be used, and in some special operating environments, need adhesive that there is fire prevention and antiacid function, it is such as acid
Substance contact, then adhesive adherence will be remarkably decreased, and glued object is detached from, and easily lead to dangerous situation.
Therefore, the adhesive that a kind of cohesive force is strong, storage stability is good, environmentally protective, biodegradable is strong is invented, is
The key to solve the above problems.
Summary of the invention
The technical problems to be solved by the invention, it is poor for current adhesive acid and alkali resistance performance while viscous for adhesive
The knot defect that performance is bad, flame retardant effect is poor, provides a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance, it is characterised in that specific preparation step are as follows:
(1) by corn stover and sodium hydroxide solution 1:15 in mass ratio investment beaker, beaker temperature is increased with resistance heating mantle
Degree, heated at constant temperature reaction, is obtained by filtration filter cake, wash with distilled water filter cake 3~5 times after reaction；
(2) according to parts by weight, 3~5 parts of above-mentioned filter cakes, 6~8 parts of ethyl orthosilicates and 30~32 parts of ethanol solutions are weighed to throw
Enter in high pressure water heating kettle, is mixed and mix products are made, pressure in high pressure water heating kettle is improved to 2.2~2.5MPa, temperature
320~340 DEG C are increased to, constant temperature and pressure reacts 60~80min, and solidliquid mixture is made；
(3) above-mentioned solidliquid mixture is put into vacuum oven, in temperature be 55~60 DEG C and vacuum degree is 30~50Pa
Under conditions of dry 15~16h, desciccate is made, the sodium stearate solution for being 10~15% by desciccate and mass fraction
1:20 in mass ratio is put into three-necked flask, three-necked flask is placed in the water-bath that bath temperature is 70~75 DEG C, constant temperature is anti-
4~5h is answered, mixed liquor is made；
(4) dichloromethane solution of the Methylaminoformyl chloride of mixed liquor quality 20~30% is added dropwise into above-mentioned three-necked flask, increases
Bath temperature is added magnetic agitation pearl into three-necked flask and reaction solution is made in condensing reflux pipe, magnetic agitation, to three-necked flask
Middle 20~25% sodium carbonate liquor of addition reaction solution quality is mixed under room temperature, modified filter residue is obtained by filtration after stirring, with steaming
Distilled water is cleaned 6~8 times；
(5) polyvinyl alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle, temperature in temperature reaction kettle, constant temperature adds
Mixed solution is made in heat, the modification filter residue after the above-mentioned cleaning of mixed solution quality 15~20% is added into reaction kettle, under constant temperature
It is mixed and prefabricated solution is made, the poly methylene poly phenyl poly isocyanate of prefabricated solution quality 3~5% is added into reaction kettle, often
Temperature is lower to be mixed, and the hydrophobic adhesive of high heat resistance acid and alkali-resistance is made.
The mass fraction of sodium hydroxide solution as described in step (1) is 20~25%, and resistance heating sleeving temperature is increased to 75
~80 DEG C, the heated at constant temperature reaction time is 2~3h.
The mass fraction of ethanol solution described in step (2) is 30~40%, and the speed of agitator in high pressure water heating kettle is
300~320r/min, mixing time are 50~60min, and pressure is improved to 2.2~2.5MPa, temperature in high pressure water heating kettle
320~340 DEG C are increased to, the constant temperature and pressure reaction time is 60~80min.
Temperature in vacuum oven described in step (3) is 55~60 DEG C, and vacuum degree is 30~50Pa, drying time
For 15~16h, the mass fraction of sodium stearate solution is 10~15%, and the bath temperature in water-bath is 70~75 DEG C, and constant temperature is anti-
It is 4~5h between seasonable.
The mass fraction of the dichloromethane solution of Methylaminoformyl chloride described in step (4) is 15~18%, bath temperature
90~100 DEG C are increased to, the speed of agitator in three-necked flask is 400~450r/min, and mixing time is 5~6h, and sodium carbonate is molten
The mass fraction of liquid is 10~12%, and the speed of agitator under room temperature is 200~220r/min, mixing time is 30~
40min。
Temperature is increased to 90~95 DEG C in reaction kettle described in step (5), and the heated at constant temperature time is 30~40min, stirs
Mixing revolving speed is 500~550r/min, and mixing time is 30~40min, and the revolving speed under room temperature is 1000~1100r/min,
Mixing time is 60~70min.
The method have the benefit that:
(1) boiling in sodium hydroxide solution by corn stover first of the invention, is obtained by filtration filter cake after boiling, by filter cake and just
Silester is mixed into horizontal high voltage hydro-thermal reaction, is concentrated and dried after reaction and desciccate is made, then by desciccate and tristearin
The mixing of acid sodium solution high temperature adds Methylaminoformyl chloride heating and is condensed back, sodium carbonate liquor reaction is added after reflux,
Modified filter residue is obtained by filtration after reaction, finally mixes modified filter residue with polyvinyl alcohol water solution and other auxiliary agents, discharging is
The hydrophobic adhesive of high heat resistance acid and alkali-resistance is obtained, corn stover is placed in boiling in lye and impregnates the plant made in corn stover by the present invention
Fiber, lignin, cellulose separation, then put into high pressure water heating kettle, it is mixed with tetraethyl orthosilicate, it is anti-to carry out high pressure hydro-thermal
It answers, decomposes plant fiber, lignin and other organic macromolecules, generate organic acid, while making the polysaccharide component in fiber
It is decomposed into monosaccharide and oligosaccharide, the hydroxyl group quantity increased in adhesive makes glue to enhance covalent bond, Hydrogen Binding Adsorption
The cementitiousness of glutinous agent is strengthened；
(2) present invention by tetraethyl orthosilicate be added high pressure hydro-thermal reaction in, tetraethyl orthosilicate under high pressure hydrothermal condition, with
The organic matters blended cross linking such as plant fiber, lignin and cellulose for being decomposed, hydrolysis gel generate coated with silica simultaneously
Oligosaccharide, monosaccharide and Determination of Organic Acids are connected, while high pressure hydro-thermal hydrolysate generated forms condensation, polycondensation reaction,
In condensation reaction, strand has access to Si-O key, while can also generate Si-C key, is conducive to the macromolecular of polycondensation generation
Chemical stability effectively improve, so that the acid-proof alkaline of adhesive be made to be improved, the present invention also utilizes stearic acid
Natrium surfactant carries out surface-active modification to each molecule in adhesive, makes to access multiple hydroxyl groups, hydroxyl on each molecule
Base group, which is then reacted with Methylaminoformyl chloride, generates ester group, and the hydrophobicity that the introducing of ester group is conducive to adhesive is improved,
Amino is introduced into each molecule of adhesive simultaneously, so that adhesive is generated ammonia when heated and blocks air, the introducing of amino
In conjunction with silica, good flame retardant effect is played, is had a good application prospect.
Specific embodiment
The sodium hydroxide solution 1:15 in mass ratio that corn stover and mass fraction are 20~25% is put into beaker, is used
Resistance heating set increases beaker temperature to 75~80 DEG C, and heated at constant temperature reacts 2~3h, filter cake is obtained by filtration after reaction, with distillation
Water cleans filter cake 3~5 times；According to parts by weight, 3~5 parts of above-mentioned filter cakes, 6~8 parts of ethyl orthosilicates and 30~32 parts are weighed
The ethanol solution that mass fraction is 30~40% is put into high pressure water heating kettle, under conditions of speed of agitator is 300~320r/min
50~60min is mixed, mix products are made, pressure in high pressure water heating kettle are improved to 2.2~2.5MPa, temperature is increased to
320~340 DEG C, constant temperature and pressure reacts 60~80min, and solidliquid mixture is made；Above-mentioned solidliquid mixture is put into and is dried in vacuo
In case, dry 15~16h, is made desciccate under conditions of temperature is 55~60 DEG C and vacuum degree is 30~50Pa, will
The sodium stearate solution 1:20 in mass ratio that desciccate and mass fraction are 10~15% is put into three-necked flask, and three mouthfuls are burnt
Bottle is placed in the water-bath that bath temperature is 70~75 DEG C, 4~5h of isothermal reaction, and mixed liquor is made；Into above-mentioned three-necked flask
The mass fraction that mixed liquor quality 20~30% is added dropwise is the dichloromethane solution of 15~18% Methylaminoformyl chlorides, increases water-bath temperature
Magnetic agitation pearl and condensing reflux pipe are added into three-necked flask to 90~100 DEG C for degree, are 400~450r/ in speed of agitator
5~6h is stirred under conditions of min, reaction solution is made, and the mass fraction that reaction solution quality 20~25% is added into three-necked flask is
10~12% sodium carbonate liquor is mixed 30~40min with the revolving speed of 200~220r/min under room temperature, filters after stirring
To modified filter residue, 6~8 times wash with distilled water；Polyvinyl alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle,
For temperature to 90~95 DEG C, mixed solution is made in 30~40min of heated at constant temperature in temperature reaction kettle, and it is molten that mixing is added into reaction kettle
Modification filter residue after the above-mentioned cleaning of liquid quality 15~20%, 30 are mixed with the revolving speed of 500~550r/min under constant temperature~
Prefabricated solution is made in 40min, and the poly methylene poly phenyl poly isocyanate of prefabricated solution quality 3~5%, room temperature are added into reaction kettle
Under revolving speed be 1000~1100r/min revolving speed under be mixed 60~70min, be made the hydrophobic gluing of high heat resistance acid and alkali-resistance
Agent.
The sodium hydroxide solution 1:15 in mass ratio that corn stover and mass fraction are 20% is put into beaker, resistance is used
Heating mantle increases beaker temperature to 75 DEG C, and heated at constant temperature reacts 2h, filter cake is obtained by filtration after reaction, wash with distilled water filter cake 3
It is secondary；According to parts by weight, the ethanol solution that 3 parts of above-mentioned filter cakes, 6 parts of ethyl orthosilicates and 30 parts of mass fractions are 30% is weighed
It puts into high pressure water heating kettle, 50min is mixed under conditions of speed of agitator is 300r/min, mix products are made, it will be high
Pressure is improved to 2.2MPa in pressure water heating kettle, and temperature is increased to 320 DEG C, and constant temperature and pressure reacts 60min, and solidliquid mixture is made；
Above-mentioned solidliquid mixture is put into vacuum oven, dry 15h under conditions of temperature is 55 DEG C and vacuum degree is 30Pa,
Desciccate is made, the sodium stearate solution 1:20 in mass ratio that desciccate and mass fraction are 10% is put into three-necked flask
In, three-necked flask is placed in the water-bath that bath temperature is 70 DEG C, isothermal reaction 4h, mixed liquor is made；It is burnt to above-mentioned three mouthfuls
The mass fraction that mixed liquor quality 20% is added dropwise in bottle is the dichloromethane solution of 15% Methylaminoformyl chloride, increases bath temperature extremely
90 DEG C, magnetic agitation pearl and condensing reflux pipe are added into three-necked flask, is stirred under conditions of speed of agitator is 400r/min
Reaction solution is made in 5h, and the mass fraction of reaction solution quality 20% is added into three-necked flask for 10% sodium carbonate liquor, under room temperature
30min is mixed with the revolving speed of 200r/min, modified filter residue is obtained by filtration after stirring, 6 times wash with distilled water；By polyethylene
Alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle, and temperature is to 90 DEG C in temperature reaction kettle, heated at constant temperature 30min system
Mixed solution, the modification filter residue after the above-mentioned cleaning of mixed solution quality 15% is added into reaction kettle, with 500r/ under constant temperature
30min is mixed in the revolving speed of min, and prefabricated solution is made, and the polymethylene polyphenyl of prefabricated solution quality 3% is added into reaction kettle
Polyisocyanates is mixed 60min in the case where revolving speed is the revolving speed of 1000r/min under room temperature, it is hydrophobic that high heat resistance acid and alkali-resistance is made
Adhesive.
The sodium hydroxide solution 1:15 in mass ratio that corn stover and mass fraction are 23% is put into beaker, resistance is used
Heating mantle increases beaker temperature to 77 DEG C, and heated at constant temperature reacts 2h, filter cake is obtained by filtration after reaction, wash with distilled water filter cake 4
It is secondary；According to parts by weight, the ethanol solution that 4 parts of above-mentioned filter cakes, 7 parts of ethyl orthosilicates and 31 parts of mass fractions are 35% is weighed
It puts into high pressure water heating kettle, 55min is mixed under conditions of speed of agitator is 310r/min, mix products are made, it will be high
Pressure is improved to 2.4MPa in pressure water heating kettle, and temperature is increased to 330 DEG C, and constant temperature and pressure reacts 70min, and solidliquid mixture is made；
Above-mentioned solidliquid mixture is put into vacuum oven, dry 15h under conditions of temperature is 57 DEG C and vacuum degree is 40Pa,
Desciccate is made, the sodium stearate solution 1:20 in mass ratio that desciccate and mass fraction are 13% is put into three-necked flask
In, three-necked flask is placed in the water-bath that bath temperature is 73 DEG C, isothermal reaction 4h, mixed liquor is made；It is burnt to above-mentioned three mouthfuls
The mass fraction that mixed liquor quality 25% is added dropwise in bottle is the dichloromethane solution of 16% Methylaminoformyl chloride, increases bath temperature extremely
95 DEG C, magnetic agitation pearl and condensing reflux pipe are added into three-necked flask, is stirred under conditions of speed of agitator is 430r/min
Reaction solution is made in 5h, and the mass fraction of reaction solution quality 23% is added into three-necked flask for 11% sodium carbonate liquor, under room temperature
35min is mixed with the revolving speed of 210r/min, modified filter residue is obtained by filtration after stirring, 7 times wash with distilled water；By polyethylene
Alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle, and temperature is to 93 DEG C in temperature reaction kettle, heated at constant temperature 35min system
Mixed solution, the modification filter residue after the above-mentioned cleaning of mixed solution quality 17% is added into reaction kettle, with 530r/ under constant temperature
35min is mixed in the revolving speed of min, and prefabricated solution is made, and the polymethylene polyphenyl of prefabricated solution quality 4% is added into reaction kettle
Polyisocyanates is mixed 65min in the case where revolving speed is the revolving speed of 1050r/min under room temperature, it is hydrophobic that high heat resistance acid and alkali-resistance is made
Adhesive.
The sodium hydroxide solution 1:15 in mass ratio that corn stover and mass fraction are 25% is put into beaker, resistance is used
Heating mantle increases beaker temperature to 80 DEG C, and heated at constant temperature reacts 3h, filter cake is obtained by filtration after reaction, wash with distilled water filter cake 5
It is secondary；According to parts by weight, the ethanol solution that 5 parts of above-mentioned filter cakes, 8 parts of ethyl orthosilicates and 32 parts of mass fractions are 40% is weighed
It puts into high pressure water heating kettle, 60min is mixed under conditions of speed of agitator is 320r/min, mix products are made, it will be high
Pressure is improved to 2.5MPa in pressure water heating kettle, and temperature is increased to 340 DEG C, and constant temperature and pressure reacts 80min, and solidliquid mixture is made；
Above-mentioned solidliquid mixture is put into vacuum oven, dry 16h under conditions of temperature is 60 DEG C and vacuum degree is 50Pa,
Desciccate is made, the sodium stearate solution 1:20 in mass ratio that desciccate and mass fraction are 15% is put into three-necked flask
In, three-necked flask is placed in the water-bath that bath temperature is 75 DEG C, isothermal reaction 5h, mixed liquor is made；It is burnt to above-mentioned three mouthfuls
The mass fraction that mixed liquor quality 30% is added dropwise in bottle is the dichloromethane solution of 18% Methylaminoformyl chloride, increases bath temperature extremely
100 DEG C, magnetic agitation pearl and condensing reflux pipe are added into three-necked flask, is stirred under conditions of speed of agitator is 450r/min
Reaction solution is made in 6h, and the mass fraction of reaction solution quality 25% is added into three-necked flask for 12% sodium carbonate liquor, under room temperature
40min is mixed with the revolving speed of 220r/min, modified filter residue is obtained by filtration after stirring, 8 times wash with distilled water；By polyethylene
Alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle, and temperature is to 95 DEG C in temperature reaction kettle, heated at constant temperature 40min system
Mixed solution, the modification filter residue after the above-mentioned cleaning of mixed solution quality 20% is added into reaction kettle, with 550r/ under constant temperature
40min is mixed in the revolving speed of min, and prefabricated solution is made, and the polymethylene polyphenyl of prefabricated solution quality 5% is added into reaction kettle
Polyisocyanates is mixed 70min in the case where revolving speed is the revolving speed of 1100r/min under room temperature, it is hydrophobic that high heat resistance acid and alkali-resistance is made
Adhesive.
The adhesive that comparative example is produced with Dongguan City company is as a comparison case to high heat resistance acid and alkali-resistance produced by the present invention
Adhesive in hydrophobic adhesive and comparative example is detected, and testing result is as shown in table 1:
Solid content test
According to standard GB/T14074-2017, measured using electric heating constant-temperature blowing drying box.
Viscosity test is measured according to standard GB/T14074-2017 using rotational viscometer.
Shear strength test according to standard HG/T2727-2010, using mechanics machine to test specimen (30mm × 25mm ×
10mm) tested.
The sulfuric acid solution that acid resistance test is 10% using concentration is added dropwise on quantitative sample, and dripping quantity is sample volume
10%, 60min after, observe sample variation.
The sodium hydroxide solution that alkaline resistance properties test is 10% using concentration is added dropwise on quantitative sample, and dripping quantity is sample
After 10%, 60min of volume, sample variation is observed.
1 performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example |
| Solid content (%) | 39.8 | 40.8 | 42.7 | 25.0 |
| The just glutinous time (s) | 23 | 21 | 20 | 36 |
| Viscosity (mPas) | 3534 | 3562 | 3581 | 2442 |
| It shears dry strength (MPa) | 10.38 | 10.43 | 10.56 | 7.64 |
| It shears wet strength (MPa) | 3.96 | 4.03 | 4.11 | 0.29 |
| Contact angle (°) | 126 | 129 | 131 | 55 |
| Acid resistance | It is unchanged | It is unchanged | It is unchanged | Generate slight erosion |
| Alkali resistance | It is unchanged | It is unchanged | It is unchanged | Generate slight erosion |
| Oxygen index (OI) (grade) | 32 | 32 | 33 | 22 |
According to data in table 1 it is found that the hydrophobic adhesive of high heat resistance acid and alkali-resistance produced by the present invention, has water-tolerant, mechanics is strong
The advantages that degree is high, and good fluidity, rate of drying is fast, and adhesive strength is high, and acid and alkali resistance ability is strong, flame retardant property is good, greatly
Cost is reduced, safety and environmental protection has wide prospect of the application.
Claims (6)
1. a kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance, it is characterised in that specific preparation step are as follows:
(1) by corn stover and sodium hydroxide solution 1:15 in mass ratio investment beaker, beaker temperature is increased with resistance heating mantle
Degree, heated at constant temperature reaction, is obtained by filtration filter cake, wash with distilled water filter cake 3~5 times after reaction；
(2) according to parts by weight, 3~5 parts of above-mentioned filter cakes, 6~8 parts of ethyl orthosilicates and 30~32 parts of ethanol solutions are weighed to throw
Enter in high pressure water heating kettle, is mixed and mix products are made, pressure in high pressure water heating kettle is improved to 2.2~2.5MPa, temperature
320~340 DEG C are increased to, constant temperature and pressure reacts 60~80min, and solidliquid mixture is made；
(3) above-mentioned solidliquid mixture is put into vacuum oven, in temperature be 55~60 DEG C and vacuum degree is 30~50Pa
Under conditions of dry 15~16h, desciccate is made, the sodium stearate solution for being 10~15% by desciccate and mass fraction
1:20 in mass ratio is put into three-necked flask, three-necked flask is placed in the water-bath that bath temperature is 70~75 DEG C, constant temperature is anti-
4~5h is answered, mixed liquor is made；
(4) dichloromethane solution of the Methylaminoformyl chloride of mixed liquor quality 20~30% is added dropwise into above-mentioned three-necked flask, increases
Bath temperature is added magnetic agitation pearl into three-necked flask and reaction solution is made in condensing reflux pipe, magnetic agitation, to three-necked flask
Middle 20~25% sodium carbonate liquor of addition reaction solution quality is mixed under room temperature, modified filter residue is obtained by filtration after stirring, with steaming
Distilled water is cleaned 6~8 times；
(5) polyvinyl alcohol and distilled water 1:5 in mass ratio are added slowly in reaction kettle, temperature in temperature reaction kettle, constant temperature adds
Mixed solution is made in heat, the modification filter residue after the above-mentioned cleaning of mixed solution quality 15~20% is added into reaction kettle, under constant temperature
It is mixed and prefabricated solution is made, the poly methylene poly phenyl poly isocyanate of prefabricated solution quality 3~5% is added into reaction kettle, often
Temperature is lower to be mixed, and the hydrophobic adhesive of high heat resistance acid and alkali-resistance is made.
2. a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance according to claim 1, it is characterised in that: step
(1) mass fraction of the sodium hydroxide solution described in is 20~25%, and resistance heating sleeving temperature is increased to 75~80 DEG C, constant temperature
The heating reaction time is 2~3h.
3. a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance according to claim 1, it is characterised in that: step
(2) mass fraction of the ethanol solution described in is 30~40%, and the speed of agitator in high pressure water heating kettle is 300~320r/min,
Mixing time is 50~60min, and pressure is improved to 2.2~2.5MPa in high pressure water heating kettle, and temperature is increased to 320~340
DEG C, the constant temperature and pressure reaction time is 60~80min.
4. a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance according to claim 1, it is characterised in that: step
(3) temperature in vacuum oven described in is 55~60 DEG C, and vacuum degree is 30~50Pa, and drying time is 15~16h, firmly
The mass fraction of resin acid sodium solution is 10~15%, and the bath temperature in water-bath is 70~75 DEG C, the isothermal reaction time is 4~
5h。
5. a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance according to claim 1, it is characterised in that: step
(4) mass fraction of the dichloromethane solution of the Methylaminoformyl chloride described in is 15~18%, bath temperature is increased to 90~
100 DEG C, the speed of agitator in three-necked flask is 400~450r/min, and mixing time is 5~6h, the quality point of sodium carbonate liquor
Number is 10~12%, and the speed of agitator under room temperature is 200~220r/min, and mixing time is 30~40min.
6. a kind of preparation method of hydrophobic adhesive of high heat resistance acid and alkali-resistance according to claim 1, it is characterised in that: step
(5) temperature is increased to 90~95 DEG C in the reaction kettle described in, and the heated at constant temperature time is 30~40min, and speed of agitator is 500~
550r/min, mixing time are 30~40min, and the revolving speed under room temperature is 1000~1100r/min, and mixing time is
60~70min.
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| CN201811078546.3A CN109266287A (en) | 2018-09-17 | 2018-09-17 | A kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance |
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| CN201811078546.3A CN109266287A (en) | 2018-09-17 | 2018-09-17 | A kind of preparation method of the hydrophobic adhesive of high heat resistance acid and alkali-resistance |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114933459A (en) * | 2022-06-15 | 2022-08-23 | 盐城市福奇混凝土有限公司 | High-performance recycled concrete and preparation method thereof |
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| CN105368369A (en) * | 2015-11-23 | 2016-03-02 | 苏州盖德精细材料有限公司 | Method for preparing polyurethane adhesive used for timber |
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