CN105906766A - Preparation method of light/biological dual-degradation high-water-absorption resin based on natural polymer - Google Patents
Preparation method of light/biological dual-degradation high-water-absorption resin based on natural polymer Download PDFInfo
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention relates to a preparation method of light/biological dual-degradation high-water-absorption resin based on natural polymer. According to the method, with cyclohexane as the solvent, a Span-series surface active agent as the dispersing agent, potassium persulfate as the initiator and N,N-methylenebis acrylamide as the crosslinking agent, by means of a reverse-phase suspension polymerization method, starch or carboxymethylcellulose or chitosan or other natural polymer reacts with acrylic acid and acrylamide monomer to prepare the light/biological dual-degradation high-water-absorption resin. According to the high-water-absorption resin, with natural polymer as the biological degradation source and nanometer TiO2 particles as the light degradation source, the nanometer TiO2 particles are evenly distributed in the high-water-absorption resin, the problem that ordinary high-water-absorption resin is difficult to degrade can be effectively solved, and the environment pollution problem is solved.
Description
Technical field
The present invention relates to High hydrophilous resin field of material technology, be specifically related to a kind of light based on natural polymer/bio-degradable high
The preparation method of water-absorbing resin.
Background technology
High hydrophilous resin also known as high water absorbency polymer (Super Absorbent Polymer, be called for short SAP), be a kind of containing carboxyl,
Strongly hydrophilic groups such as hydroxyl and there is the high molecular polymer of highly cross-linked water absorption and swelling type tridimensional network.High water suction
Property resin the absorbable greatly distilled water reaching hundreds and thousands of times of own wt of water absorption, after water suction, its water retention property is the strongest, even if
Also being not easy dehydration under heating, pressurized conditions, the stability in acid, alkali environment is the most fine.
The eighties in 20th century, some natural high molecular substances (such as starch, cellulose, chitosan etc.) preparation height is utilized to inhale
The research of water-resin composite starts appearance, and along with the addition of these natural products, the performance of super absorbent resin resin composite material has
Great improvement, has expanded its application.But the High hydrophilous resin degraded by simple natural polymer grafting preparation
Degree is the highest, has residue after degraded, and introducing has the inorganic material of degradation property can increase its degradation efficiency.There is document
It is reported in resins synthesis and adds the TiO 2 sol organised and can improve the degradation efficiency of material, but final degradation efficiency is not
High；Also have after resins synthesis and the degradation property that improve material is blended with nano titanium oxide nanoparticle, but nanometer titanium dioxide
Titanium is only attached to resin surface, and only the initial stage in degraded plays a role, and the degradation property of this material is the most not ideal enough.At material
The preparation process of material introduces titanium dioxide nanoparticle, it is possible to more uniform dispersed titanium dioxide nano-particle, improve light fall
Solve efficiency.
Summary of the invention
It is an object of the invention to solve the deficiency such as existing super absorbent resin material degradation poor performance, degraded mode be single, it is provided that
The preparation method of a kind of light based on natural polymer/bio-degradable High hydrophilous resin, the method uses natural polymer to be substrate
And add titanium dioxide nanoparticle and synthesized compound High hydrophilous resin, significantly enhance degradation efficiency, decrease environment
Pollute.
The technical scheme is that the preparation method of a kind of light based on natural polymer/bio-degradable High hydrophilous resin, bag
Include following steps:
(1) sodium hydroxide solution is joined in acrylic acid solution, is configured to the acrylic acid solution of certain degree of neutralization, then to
Solution adds a certain amount of potassium peroxydisulfate, N,N methylene bis acrylamide and acrylamide, is sufficiently stirred for obtaining mixed solution；
(2) a certain amount of Span (span) surfactant is dissolved in equipped with in the reactor of hexamethylene, adds a certain amount of
Natural polymer and nano titanium oxide, stirring heat temperature raising, in reactor, it is filled with protective gas；
(3) step (1) gained mixed solution is added dropwise in reactor, heats up after dropping and react, reaction
Through filtration, washing, drying light/bio-degradable High hydrophilous resin after completing.
Preferably, the acrylic acid after decompression distillation is first dissolved in water by step (1), then acrylic acid solution is placed in ice-water bath
Under add sodium hydroxide solution while stirring, being neutralized to degree of neutralization is to make solution be warmed to room temperature after 60-80%.
Preferably, step is heated to 45-70 DEG C in (2), and described Span surfactant is Span20, Span40,
One in Span60, Span80, Span65, Span85, the protective gas being passed through is nitrogen or argon.
Preferably, being warming up to 60-85 DEG C and react in step (3), the response time is 1-4h, and product uses nothing after filtering
Water-ethanol or anhydrous propanone washing.
According to such scheme, described natural polymer one in starch, carboxymethyl cellulose or chitosan.
According to such scheme, each reactant consumption is counted by weight and is included 8-10 part acrylic acid, 0.06-0.1 part potassium peroxydisulfate,
0.008-0.01 part N,N methylene bis acrylamide, 1.5-2 part acrylamide, 0.8-1 part Span surfactant, 100
Part hexamethylene, 1 part of natural polymer and 1 part of nano titanium oxide.
According to such scheme, optimum synthesis condition is: each reactant consumption is counted by weight and included 9 parts of acrylic acid, 0.08
Part potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide, 1.6 parts of acrylamides, 0.9 part of Span80 surfactant,
100 parts of hexamethylene, 1 part of carboxymethyl cellulose and 1 part of nano titanium oxide, the degree of neutralization of step (1) gained acrylic acid solution
Being 70%, in step (2), agitating heating is warming up to 50 DEG C, reaction temperature 70 DEG C, response time 3h in step (3).
The inventive method has the effect that the High hydrophilous resin water absorbent rate (1) prepared is up to thousands of times, and rate of water absorption is fast；
(2) addition of natural polymer enhances the biocompatibility of High hydrophilous resin, can be applicable to biological field；(3) sky is used
So polymer substance is as biodegradation source, nano-TiO2Particle is light degradation source, has prepared and has had light degradation and life simultaneously
The High hydrophilous resin of thing degradation property, decreases the problem of environmental pollution of High hydrophilous resin；(4) reaction condition is the gentleest, system
Standby technique is simple；(5) resin prepared by inverse suspension method is in granular form, and will not form gel, and post processing is more convenient；(6) nanometer
Titanium dioxide granule specific surface area is big, and it is uniformly distributed in High hydrophilous resin after being wrapped up by resin, than simple and resin alloy
There is higher degradation efficiency.
Detailed description of the invention
For making those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specific embodiment
It is further detailed.
Embodiment 1
(1) by soluble in water for the acrylic acid after 10 parts of (parts by weight meter, lower same) decompression distillations, solution is put into conical flask
Being placed in ice-water bath, add NaOH solution with constant voltage separatory funnel under magnetic agitation in conical flask, being made into degree of neutralization is 75%
Acrylic acid solution.0.06 part of potassium peroxydisulfate, 0.008 part of N, N-methylene bisacrylamide is added after acrylic acid solution is warmed to room temperature
Amide and 1.5 parts of acrylamides, be thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of starch and 1 part of nano-titania particle, stir and heat up
To 45 DEG C, it is filled with nitrogen and keeps four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 838.3g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water；365
Under the conditions of nm ultraviolet degradation, within 72 hours, resin degradation rate is more than 60%；Under soil environment, within 60 days, resin degradation rate exceedes
50%.
Embodiment 2
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.08 part of potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide and 1.75 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.9 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of starch and 1 part of nano-titania particle, stir and heat up
To 45 DEG C, it is filled with nitrogen and keeps four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 878.3g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales quality
The multiplying power of mark 0.9% saline (sodium-chloride water solution) is 92.9g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours resins
Degradation rate is more than 60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 3
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.1 part of potassium peroxydisulfate, 0.01 part of N,N methylene bis acrylamide and 2.0 parts of acrylamides after being warmed to room temperature,
It is thoroughly mixed uniform mixed solution.
(2) 1.0 parts of sorbester p17s are substantially dissolved in 100 parts of hexamethylene, are proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of starch and 1 part of nano-titania particle, stir and heat up
To 45 DEG C, it is filled with nitrogen and keeps four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1078.8g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 127.7g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours
Resin degradation rate is more than 60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 4
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 45 DEG C, be filled with nitrogen and keep four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1161.8g/g that resin prepared by the present embodiment sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 80.7g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours trees
Fat degradation rate is more than 60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 5
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.08 part of potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide and 1.75 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.9 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 45 DEG C, be filled with nitrogen and keep four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1300.4g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 135.1g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 6
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.1 part of potassium peroxydisulfate, 0.01 part of N,N methylene bis acrylamide and 2.0 parts of acrylamides after being warmed to room temperature,
It is thoroughly mixed uniform mixed solution.
(2) 1.0 parts of sorbester p17s are substantially dissolved in 100 parts of hexamethylene, are proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 45 DEG C, be filled with nitrogen and keep four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1747.4g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 83.6g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 7
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of chitosan and 1 part of nano-titania particle, stir and rise
Temperature, to 45 DEG C, is filled with nitrogen and keeps being in four-hole boiling flask nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1197.3g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 99.6g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 8
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.08 part of potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide and 1.75 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.9 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of chitosan and 1 part of nano-titania particle, stir and rise
Temperature, to 45 DEG C, is filled with nitrogen and keeps being in four-hole boiling flask nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1471.5g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 88.8g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 9
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 75%.Treat third
Olefin(e) acid solution adds 0.1 part of potassium peroxydisulfate, 0.01 part of N,N methylene bis acrylamide and 2.0 parts of acrylamides after being warmed to room temperature,
It is thoroughly mixed uniform mixed solution.
(2) 1.0 parts of sorbester p17s are substantially dissolved in 100 parts of hexamethylene, are proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of chitosan and 1 part of nano-titania particle, stir and rise
Temperature, to 45 DEG C, is filled with nitrogen and keeps being in four-hole boiling flask nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 75 DEG C after dropping instead
Answer 2h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1571.9g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 68.8g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
60%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 10
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 60%.Treat third
Olefin(e) acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p18 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 70 DEG C, be filled with argon and keep four-hole boiling flask is in argon atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 85 DEG C after dropping instead
Answer 1h.Solution is filtered after terminating by reaction, and filtering residue anhydrous propanone washes twice, and is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1341.8g/g that resin prepared by the present embodiment sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline is 88.7g/g；Under the conditions of 365nm ultraviolet degradation, within 72 hours, resin degradation rate exceedes
70%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 11
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 80%.Treat third
Olefin(e) acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p37 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 60 DEG C, be filled with argon and keep four-hole boiling flask is in argon atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 85 DEG C after dropping instead
Answer 4h.Solution is filtered after terminating by reaction, and filtering residue anhydrous propanone washes twice, and is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1235.3g/g that resin prepared by the present embodiment sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 92.1g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours trees
Fat degradation rate is more than 70%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 12
(1) by soluble in water for the acrylic acid after 10 parts of decompression distillations, solution is put into conical flask and is placed in ice-water bath, magnetic force
Stirring is lower adds NaOH solution with constant voltage separatory funnel in conical flask, is made into the acrylic acid solution that degree of neutralization is 70%.Treat third
Olefin(e) acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acryloyls after being warmed to room temperature
Amine, is thoroughly mixed uniform mixed solution.
(2) 0.8 part of span 40 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 60 DEG C, be filled with argon and keep four-hole boiling flask is in argon atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 85 DEG C after dropping instead
Answer 4h.Solution is filtered after terminating by reaction, and filtering residue anhydrous propanone washes twice, and is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1235.3g/g that resin prepared by the present embodiment sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 92.1g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours trees
Fat degradation rate is more than 70%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 13
(1) by soluble in water for the acrylic acid after 8 parts of decompression distillations, solution being put into conical flask and is placed in ice-water bath, magnetic force stirs
Mix lower constant voltage separatory funnel in conical flask, add NaOH solution, be made into the acrylic acid solution that degree of neutralization is 65%.Treat propylene
Acid solution adds 0.06 part of potassium peroxydisulfate, 0.008 part of N,N methylene bis acrylamide and 1.5 parts of acrylamides after being warmed to room temperature,
It is thoroughly mixed uniform mixed solution.
(2) 0.8 part of sorbester p38 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 50 DEG C, be filled with argon and keep four-hole boiling flask is in argon atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, is warming up to 85 DEG C after dropping instead
Answer 4h.Solution is filtered after terminating by reaction, and filtering residue anhydrous propanone washes twice, and is subsequently placed in baking oven drying, slightly mills
Obtain light/bio-degradable High hydrophilous resin.It is 1131.3g/g that resin prepared by the present embodiment sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 90.1g/g；Under the conditions of 365nm ultraviolet degradation, 72 hours trees
Fat degradation rate is more than 65%；Under soil environment, within 60 days, resin degradation rate is more than 50%.
Embodiment 14
(1) by soluble in water for the acrylic acid after 9 parts of decompression distillations, solution being put into conical flask and is placed in ice-water bath, magnetic force stirs
Mix lower constant voltage separatory funnel in conical flask, add NaOH solution, be made into the acrylic acid solution that degree of neutralization is 70%.Treat propylene
Acid solution adds 0.08 part of potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide and 1.6 parts of acrylamides after being warmed to room temperature,
It is thoroughly mixed uniform mixed solution.
(2) 0.9 part of sorbester p17 is substantially dissolved in 100 parts of hexamethylene, is proceeded to be furnished with mechanical agitation, reflux condensation mode
In the four-hole boiling flask of pipe, thermometer and airway, add 1 part of carboxymethyl cellulose and 1 part of nano-titania particle, stir
Mix and be warming up to 50 DEG C, be filled with nitrogen and keep four-hole boiling flask is in nitrogen atmosphere.
(3) (1) gained mixed solution is added dropwise in (2) in four-hole boiling flask, after dropping, is warming up to 70 DEG C of reactions
3h.Solution is filtered after terminating by reaction, filtering residue absolute ethanol washing twice, is subsequently placed in baking oven drying, slightly mills i.e.
Obtain light/bio-degradable High hydrophilous resin.It is 1621.3g/g that the resin that the present embodiment prepares sucks the multiplying power of ionized water, inhales matter
The multiplying power of amount mark 0.9% saline (sodium-chloride water solution) is 102.7g/g；Under the conditions of 365nm ultraviolet degradation, 72 is little
Time resin degradation rate more than 70%；Under soil environment, within 60 days, resin degradation rate is more than 60%.
Claims (7)
1. the preparation method of light based on natural polymer/bio-degradable High hydrophilous resin, it is characterised in that include following step
Rapid:
(1) sodium hydroxide solution is joined in acrylic acid solution, is configured to the acrylic acid solution of certain degree of neutralization, then to
Solution adds a certain amount of potassium peroxydisulfate, N,N methylene bis acrylamide and acrylamide, is sufficiently stirred for obtaining mixed solution；
(2) a certain amount of Span surfactant is dissolved in equipped with in the reactor of hexamethylene, adds a certain amount of natural polymer
Son and nano titanium oxide, stirring heat temperature raising, in reactor, it is filled with protective gas；
(3) step (1) gained mixed solution is added dropwise in reactor, heats up after dropping and react, reaction
Through filtration, washing, drying light/bio-degradable High hydrophilous resin after completing.
2. the preparation method of light/bio-degradable High hydrophilous resin as claimed in claim 1, it is characterised in that: in step (1) first
Acrylic acid after decompression distillation is dissolved in water, then acrylic acid solution is placed under ice-water bath to add sodium hydroxide while stirring molten
Liquid, being neutralized to degree of neutralization is to make solution be warmed to room temperature after 60-80%.
3. the preparation method of light/bio-degradable High hydrophilous resin as claimed in claim 1, it is characterised in that: step adds in (2)
Heat is warming up to 45-70 DEG C, and Span surfactant is Span20, Span40, Span60, Span80, Span65, Span85
In one, the protective gas being passed through is nitrogen or argon.
4. the preparation method of light/bio-degradable High hydrophilous resin as claimed in claim 1, it is characterised in that: step (3) rises
Temperature is reacted to 60-85 DEG C, and the response time is 1-4h, and product is washed with dehydrated alcohol or anhydrous propanone after filtering.
5. the preparation method of the light as described in any one of claim 1-4/bio-degradable High hydrophilous resin, it is characterised in that: described
Natural polymer one in starch, carboxymethyl cellulose or chitosan.
6. the preparation method of the light as described in any one of claim 1-4/bio-degradable High hydrophilous resin, it is characterised in that: each instead
Answer thing consumption to count by weight and include 8-10 part acrylic acid, 0.06-0.1 part potassium peroxydisulfate, 0.008-0.01 part N, N-methylene
Bisacrylamide, 1.5-2 part acrylamide, 0.8-1 part Span surfactant, 100 parts of hexamethylene, 1 part of natural polymer
With 1 part of nano titanium oxide.
7. the preparation method of light/bio-degradable High hydrophilous resin as claimed in claim 1, it is characterised in that: each reactant consumption is pressed
Parts by weight meter includes 9 parts of acrylic acid, 0.08 part of potassium peroxydisulfate, 0.009 part of N,N methylene bis acrylamide, 1.6 parts of propylene
Amide, 0.9 part of Span80 surfactant, 100 parts of hexamethylene, 1 part of carboxymethyl cellulose and 1 part of nano titanium oxide,
In step (1), the degree of neutralization of acrylic acid solution is 70%, and in step (2), agitating heating is warming up to 50 DEG C, in step (3)
Reaction temperature 70 DEG C, response time 3h.
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| CN116283027A (en) * | 2023-02-03 | 2023-06-23 | 北京市政建设集团有限责任公司 | Engineering soil water reducing agent with high water content, preparation method and application thereof |
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| CN106883350A (en) * | 2017-03-07 | 2017-06-23 | 吴肖颜 | A kind of preparation method of degradable high-efficiency water-absorbing resin |
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| CN109535495A (en) * | 2018-11-13 | 2019-03-29 | 浙江金晟环保股份有限公司 | Biodegradable water-absorbent material of biocidal property for chilled food and preparation method thereof |
| CN116283027A (en) * | 2023-02-03 | 2023-06-23 | 北京市政建设集团有限责任公司 | Engineering soil water reducing agent with high water content, preparation method and application thereof |
| CN116283027B (en) * | 2023-02-03 | 2024-05-10 | 北京市政建设集团有限责任公司 | Engineering soil water reducing agent with high water content, preparation method and application thereof |
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