CN107057251B - A kind of Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin and preparation method thereof - Google Patents
A kind of Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin and preparation method thereof Download PDFInfo
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Abstract
A kind of Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin, it is made according to 1 ︰ of mass ratio, 0.005~0.04 ︰, 0.0001~0.0005 ︰ 0.02~0.04 by photopolymerization by acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent N, N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone etc..Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin method provided by the invention for preparing has the characteristics that reaction condition is mild, easy to operate, easy to implement.Sodium Polyacrylate provided by the invention/nano cellulose crystal composite high-water-absorptivresin resin Water absorption inhales physiological saline multiple up to 71~139g/g up to 1200~3000g/g.Meanwhile the composite high-water-absorptivresin resin has pore structure abundant, is conducive to improve water suction or physiological saline rate.The invention discloses its preparation methods.
Description
Technical field
The invention belongs to super absorbent resin technical fields, and in particular to a kind of Sodium Polyacrylate/nano cellulose crystal
Composite high-water-absorptivresin resin and preparation method thereof.
Background technique
Super absorbent resin is a kind of functional polymer material that can be absorbed and keep sole mass hundred times to thousands of times,
It is widely used in the fields such as agriculture and forestry, industry, building and health.Sodium Polyacrylate Super Hydroscopicity Resin is a kind of important synthesis
Super absorbent resin, it has many advantages, such as, and synthesis technology is simple, Water absorption is high, security performance is preferable, product matter is not surely corrupt,
It is widely studied and applied.However, Sodium Polyacrylate Super Hydroscopicity Resin also exists, salt tolerance is poor, rate of water absorption is not fast enough, inhales
The disadvantages such as intensity is low after water, it is necessary to disadvantages mentioned above be overcome by modification, be just able to satisfy super absorbent resin in different application
Needs.
Currently, carrying out nano combined being a kind of important change to Sodium Polyacrylate Super Hydroscopicity Resin with various nano materials
Property method, mainly using the inorganic nano materials such as book clay, metal/non-metal oxide-based nanomaterial, carbon nanotube (ginseng
See: New Chemical Materials, 2016,44 (2): 43-45；Applied chemistry, 2017,34 (3): 282-290).It is nano-compound modified logical
The gel network structure of super absorbent resin can often be changed, so as to improve the performance of resin.For example, nano combined high-hydroscopicity tree
Pore structure inside rouge increase be beneficial to improve water absorption rate and rate of water absorption (referring to fine chemistry industry, 2017,34 (2):
145–151；Macromolecule journal, 2013,9:1183-1189), the physical/chemical between nano particle and super absorbent resin matrix
Interaction is then conducive to improve gel strength and thermal stability etc..To prepare nano combined Sodium Polyacrylate high-hydroscopicity tree
Nano material is generally first evenly dispersed in sodium acrylate/acrylic acid mix monomer aqueous solution by rouge, then by situ poly-
The method of conjunction obtains Super-absorbent nanocomposite (referring to CN 101787101B, CN 105482024A, CN
103360543A, applied chemistry, 2017,34 (3): 282-290)；Therefore, nano material is dispersed in propylene with must be stable to
In sour sodium/acrylic acid mix monomer aqueous solution.
Nano cellulose crystal is the rod-like nano particle of a kind of 5~20nm of diameter, long 100~1000nm, can be by strong
The various celluloses of sour water solution are made, it has, and intensity is high, specific gravity is small, it is modified, compatible with water-soluble polymeric matrix to be easy to surface
The advantages that property is good is highly suitable for the nano-compound modified (referring to Journal of Applied of super absorbent resin
Polymer Science,2014,131(2):39725-39737).Currently, nano cellulose crystal majority is by sulphuric acid hydrolysis fibre
Dimension element is made, and surface has sulfate group (- OSO3 ?), be conducive to the stable dispersion of nano cellulose crystal in water；But
If nano cellulose crystal is added in strong electrolyte aqueous solution, it is possible to create flocculate and cannot uniformly and stably disperse.It is yellow
Bacteria cellulose whisker and sodium acrylate/acrylic acid/acrylamide are mixed in ocean etc. (macromolecule journal, 2013,9:1183-1189)
Closing monomer, in-situ polymerization is prepared for bacteria cellulose whisker/poly- (acrylic acid-acrylamide) composite high-water-absorptivresin resin together, sends out
Water suction and the physiological saline multiple of resin can be improved when now only adding the bacteria cellulose whisker of a small amount of (0.05wt%)；Study carefully
Its reason is primarily due to point of the bacteria cellulose whisker in sodium acrylate/acrylic acid/acrylamide mix monomer aqueous solution
Scattered stability be not it is very good, bacteria cellulose whisker is easy for reuniting when additive amount is slightly larger, drops the water absorbing properties of resin
It is low.Exactly because nano cellulose crystal cannot uniformly and stably disperse in sodium acrylate/acrylic acid mix monomer aqueous solution
(referring to Fig. 1 (a)) has no mix nano cellulose crystal or modified nanometer cellulose crystal with sodium acrylate/acrylic acid at present
Closing monomer, in-situ polymerization prepares the report of Super-absorbent nanocomposite together.
To improve dispersion stabilization of the nano cellulose crystal in electrolyte solution, a kind of feasible method be to its into
Row surface graft modification.For example, (Journal of Functional Polymers, 2016,29 (3): 323-328) to nano-cellulose crystalline substance such as Yan Dedong
After body carries out surface cationic, dispersion stabilization of the nano cellulose crystal in chitosan-acetic acid solution is improved.
Summary of the invention
It is an object of the invention to provide a kind of Sodium Polyacrylate/nano-cellulose in place of overcome the deficiencies in the prior art
Crystal composite high-water-absorptivresin resin, its Water absorption with higher and suction physiological saline multiple, salt tolerance are improved.Together
When, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin has more than Sodium Polyacrylate Super Hydroscopicity Resin
Pore structure (referring to fig. 2) abundant is conducive to improve water suction or physiological saline rate.
Another object of the present invention is to provide above-mentioned Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resins
Preparation method.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin, it includes following step
It is rapid:
The preparation of step 1. nano cellulose crystal:
Microcrystalline cellulose is dispersed in the sulfuric acid that mass concentration is 63~65%, the liquid of sulfuric acid and microcrystalline cellulose
Gu being then stirred to react at 40~45 DEG C 1.5~2 hours than being 10~14mL/g；After reaction, under stiring by product
It is added in the deionized water of 10~12 times of its volumes, is centrifugated and then obtains paste through 3~4 repetition water washings,
The content of middle nano cellulose crystal is 10 ± 1wt%；
The preparation of step 2. nano cellulose crystal-g- polyacrylamide:
In deionized water by the dispersion of nano cellulose crystal paste obtained by step 1, make nano cellulose crystal
Concentration be 1~2%g/mL, and adjust solution ph to 2~3 with nitric acid；Then lead to 20~30min of nitrogen air is discharged,
Ammonium ceric nitrate is added after being warming up to 45~50 DEG C, acrylamide is added after being stirred to react 10min, and continue anti-in a nitrogen atmosphere
It answers 4~6 hours, the concentration of the ammonium ceric nitrate is 4~6mmol/L, the quality of acrylamide is nano cellulose crystal quality
2~3 times；After completion of the reaction, product is fitted into dialysis in bag filter and removes (the cerium salt initiation of the substances such as unreacted acrylamide
When hardly generate polyacrylamide homo polymer), obtain nano cellulose crystal-g- polyacrylamide solution, wherein nanometer
The content of cellulose crystals-g- polyacrylamide is 1.5~3wt%.
The preparation of step 3. Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin:
Acrylic acid is neutralized to in ice-water bath with the sodium hydrate aqueous solution of concentration 20%g/mL 60% degree of neutralization, it is cold
But nano cellulose crystal-g- polyacrylamide solution obtained by a certain amount of water, step 2, the Asia crosslinking agent N, N'- are added afterwards
Bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and uniform solution is stirred into,
Make the concentration 20%g/mL of acrylic acid, the quality of the nano cellulose crystal-g- polyacrylamide is acrylic acid quality
0.005~0.04 times, the quality of crosslinking agent is 0.0001~0.0005 times of acrylic acid quality, and the quality of photoinitiator is propylene
0.02~0.04 times of sour quality；Then acquired solution is poured into container, makes 3~5mm of liquid level, and use wavelength for
The high-pressure sodium lamp that 365nm, power are 500~1000w is ultraviolet source, is gathered after 20~40min of photopolymerization at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin is crossed 60 meshes by product drying obtained, after mechanical crushing and is obtained
To final products.
Poly- the third of the preparation method preparation of a kind of above-mentioned Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin
Olefin(e) acid sodium/nano cellulose crystal composite high-water-absorptivresin resin.
Sodium Polyacrylate of the invention/nano cellulose crystal composite high-water-absorptivresin resin is according to People's Republic of China's agriculture
Method in industry professional standard NY886-2010 " agricultural water-retaining agent " is reachable to measure water suction and physiological saline multiple, Water absorption
1200~3000g/g inhales physiological saline multiple up to 71~139g/g.
The present invention have the following advantages compared with the existing technology and the utility model has the advantages that
It is (1) provided by the invention to prepare in Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin method,
By the surface graft modification to nano cellulose crystal, it is made to be dispersed stably in sodium acrylate/acrylic acid mix monomer water
(referring to Fig. 1 (b)) in solution, solve point of the nano cellulose crystal in sodium acrylate/acrylic acid mix monomer aqueous solution
Dissipate stability problem.
(2) provided by the invention to prepare Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin method tool
Have the characteristics that reaction condition is mild, easy to operate, easy to implement.
(3) Sodium Polyacrylate provided by the invention/nano cellulose crystal composite high-water-absorptivresin resin suction with higher
Water multiple and suction physiological saline multiple, salt tolerance are improved.Meanwhile the composite high-water-absorptivresin resin has hole abundant
Structure is conducive to improve water suction or physiological saline rate.
Detailed description of the invention
Fig. 1 is nano cellulose crystal (NCC) and nano cellulose crystal-g- polyacrylamide (NCC-g-PAM) third
Dispersion picture in olefin(e) acid sodium/acrylic acid mix monomer aqueous solution: (a) acrylic acid (AA, 60% neutralization of 20%w/v
Degree)+0.2%w/w (NCC/AA) NCC, (b) acrylic acid (AA, 60% degree of neutralization)+2%w/w (NCC-g- of 20%w/v
PAM/AA NCC-g-PAM).
Fig. 2 is sweeping after Sodium Polyacrylate of the invention/nano cellulose crystal composite high-water-absorptivresin resin is freeze-dried
Retouch electromicroscopic photograph.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but the embodiment invented is not limited to
This.
Embodiment 1
One, the preparation of nano cellulose crystal
7g microcrystalline cellulose is dispersed in the sulfuric acid that 100mL mass concentration is 64%, is then stirred at 45 DEG C
Reaction 1.5 hours；After reaction, product is added under stiring in the deionized water of 1000mL, then centrifuge separation passes through
4 times repetition water washing obtains paste, and wherein the content of nano cellulose crystal is 10wt% or so.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
Taking appropriate above-mentioned nano cellulose crystal paste dispersion to obtain 100mL concentration in deionized water is 1%g/mL's
Solution, and adjusting solution ph with nitric acid is 2；Then lead to nitrogen 30min so that air is discharged, 0.33g is added after being warming up to 45 DEG C
3g acrylamide is added after being stirred to react 10min in ammonium ceric nitrate, and continues to react 4 hours in a nitrogen atmosphere.End of reaction
Afterwards, product is fitted into dialysis in bag filter and removes the substances such as unreacted acrylamide, obtain nano cellulose crystal-g- poly- third
Acrylamide aqueous solution, wherein the content of nano cellulose crystal-g- polyacrylamide is 1.5wt%.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.005 ︰, 0.00025 ︰ 0.04；Then acquired solution is poured into container, makes liquid level 3mm,
And the high-pressure sodium lamp for using wavelength to be 1000w for 365nm, power is ultraviolet source, is obtained after photopolymerization 20min at room temperature
Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin.By product drying obtained, 60 meshes are crossed after mechanical crushing
Obtain final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 3000g/g, suction physiological saline multiple are 139g/g.
Embodiment 2
One, the preparation of nano cellulose crystal
The preparation of nano cellulose crystal is the same as embodiment 1 in the present embodiment.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
The preparation of nano cellulose crystal-g- polyacrylamide is the same as embodiment 1 in the present embodiment.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.01 ︰, 0.00025 ︰ 0.04；Then acquired solution is poured into container, makes liquid level 4mm, and
The high-pressure sodium lamp for using wavelength to be 1000w for 365nm, power is ultraviolet source, is gathered after photopolymerization 30min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 1796g/g, suction physiological saline multiple are 104g/g.
Embodiment 3
One, the preparation of nano cellulose crystal
The preparation of nano cellulose crystal is the same as embodiment 1 in the present embodiment.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
The preparation of nano cellulose crystal-g- polyacrylamide is the same as embodiment 1 in the present embodiment.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.02 ︰, 0.00025 ︰ 0.04；Then acquired solution is poured into container, makes liquid level 4mm, and
The high-pressure sodium lamp for using wavelength to be 1000w for 365nm, power is ultraviolet source, is gathered after photopolymerization 30min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.Its stereoscan photograph is shown in Fig. 2.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 1200g/g, suction physiological saline multiple are 71g/g.
Embodiment 4
One, the preparation of nano cellulose crystal
10g microcrystalline cellulose is dispersed in the sulfuric acid that 100mL mass concentration is 65%, is then stirred at 45 DEG C
Reaction 2 hours；After reaction, product is added in the deionized water of 1200mL under stiring, is centrifugated, then through weight
Multiple 3 water washings obtain paste, and wherein the content of nano cellulose crystal is 10wt% or so.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
Taking appropriate above-mentioned nano cellulose crystal paste dispersion to obtain 100mL concentration in deionized water is 2%g/mL's
Solution, and adjusting solution ph with nitric acid is 3；Then lead to nitrogen 20min so that air is discharged, 0.275g is added after being warming up to 40 DEG C
5g acrylamide is added after being stirred to react 10min in ammonium ceric nitrate, and continues to react 5 hours in a nitrogen atmosphere.End of reaction
Afterwards, product is fitted into dialysis in bag filter and removes the substances such as unreacted acrylamide, obtain nano cellulose crystal-g- poly- third
Acrylamide aqueous solution, wherein the content of nano cellulose crystal-g- polyacrylamide is 3wt%.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.01 ︰, 0.0001 ︰ 0.02；Then acquired solution is poured into container, makes liquid level 4mm, and
The high-pressure sodium lamp for using wavelength to be 1000w for 365nm, power is ultraviolet source, is gathered after photopolymerization 40min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 2956g/g, suction physiological saline multiple are 136g/g.
Embodiment 5
One, the preparation of nano cellulose crystal
The preparation of nano cellulose crystal is the same as embodiment 4 in the present embodiment.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
The preparation of nano cellulose crystal-g- polyacrylamide is the same as embodiment 4 in the present embodiment.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.005 ︰, 0.0005 ︰ 0.03；Then acquired solution is poured into container, makes liquid level 3mm, and
The high-pressure sodium lamp for using wavelength to be 500w for 365nm, power is ultraviolet source, is gathered after photopolymerization 40min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 1531g/g, suction physiological saline multiple are 89g/g.
Embodiment 6
One, the preparation of nano cellulose crystal
8.5g microcrystalline cellulose is dispersed in the sulfuric acid that 100mL mass concentration is 63%, is then stirred at 40 DEG C
Mix reaction 2 hours；After reaction, product is added in the deionized water of 1100mL under stiring, is centrifugated, then passes through
It is repeated 3 times water washing and obtains paste, wherein the content of nano cellulose crystal is 10wt% or so.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
Taking appropriate above-mentioned nano cellulose crystal paste dispersion to obtain 100mL concentration in deionized water is 1.5%g/mL
Solution, and with nitric acid adjust solution ph be 2.5；Then lead to nitrogen 20min so that air is discharged, be added after being warming up to 40 DEG C
3g acrylamide is added after being stirred to react 10min in 0.22g ammonium ceric nitrate, and continues to react 6 hours in a nitrogen atmosphere.Reaction
After, product is fitted into dialysis in bag filter and removes the substances such as unreacted acrylamide, obtains nano cellulose crystal-g-
Polyacrylamide solution, wherein the content of nano cellulose crystal-g- polyacrylamide is 2.3wt%.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.04 ︰, 0.0001 ︰ 0.03；Then acquired solution is poured into container, makes liquid level 5mm, and
The high-pressure sodium lamp for using wavelength to be 500w for 365nm, power is ultraviolet source, is gathered after photopolymerization 40min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 1692g/g, suction physiological saline multiple are 96g/g.
Embodiment 7
One, the preparation of nano cellulose crystal
The preparation of nano cellulose crystal is the same as embodiment 6 in the present embodiment.
Two, the preparation of nano cellulose crystal-g- polyacrylamide
The preparation of nano cellulose crystal-g- polyacrylamide is the same as embodiment 6 in the present embodiment.
Three, Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation
With the sodium hydrate aqueous solution of concentration 20%g/mL 10g acrylic acid is neutralized in 60% in ice-water bath and
Nano cellulose crystal-g- polyacrylamide solution, crosslinking agent N obtained by suitable water, step 2 is added after cooling in degree,
N'- methylene-bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and stir into uniform
Solution, makes the concentration 20%g/mL of acrylic acid, and acrylic acid, nano cellulose crystal-g- polyacrylamide, crosslinking agent, light draw
The mass ratio for sending out agent is 1 ︰, 0.01 ︰, 0.0005 ︰ 0.02；Then acquired solution is poured into container, makes liquid level 5mm, and
The high-pressure sodium lamp for using wavelength to be 1000w for 365nm, power is ultraviolet source, is gathered after photopolymerization 40min at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin.60 meshes are crossed by product drying obtained, after mechanical crushing to obtain
To final products.
Suction is measured according to the method in People's Republic of China (PRC) agricultural industry criteria NY886-2010 " agricultural water-retaining agent "
Water and physiological saline multiple, Water absorption 1271g/g, suction physiological saline multiple are 73g/g.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (2)
1. a kind of Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin preparation method, it is characterized in that it includes
Following steps:
The preparation of step 1. nano cellulose crystal:
Microcrystalline cellulose is dispersed in the sulfuric acid that mass concentration is 63~65%, the liquid-solid ratio of sulfuric acid and microcrystalline cellulose
For 10~14mL/g, then it is stirred to react at 40~45 DEG C 1.5~2 hours；After reaction, product is added under stiring
Into the deionized water of 10~12 times of its volumes, it is centrifugated and then obtains paste through 3~4 repetition water washings, wherein receiving
The content of rice cellulose crystals is 10 ± 1wt%；
The preparation of step 2. nano cellulose crystal-g- polyacrylamide:
In deionized water by the dispersion of nano cellulose crystal paste obtained by step 1, make the dense of nano cellulose crystal
Degree is 1~2%g/mL, and adjusts solution ph to 2~3 with nitric acid；Then lead to 20~30min of nitrogen so that air is discharged, heat up
Ammonium ceric nitrate is added after to 45~50 DEG C, acrylamide is added after being stirred to react 10min, and continue to react 4 in a nitrogen atmosphere
~6 hours, the concentration of the ammonium ceric nitrate is 4~6mmol/L, the quality of acrylamide is nano cellulose crystal quality 2
~3 times；After completion of the reaction, product is fitted into dialysis in bag filter and removes unreacted acrylamide, obtain nano-cellulose crystalline substance
Body-g- polyacrylamide solution, wherein the content of nano cellulose crystal-g- polyacrylamide is 1.5~3wt%；
The preparation of step 3. Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin:
Acrylic acid is neutralized to in ice-water bath with the sodium hydrate aqueous solution of concentration 20%g/mL 60% degree of neutralization, after cooling
Nano cellulose crystal-g- polyacrylamide solution obtained by a certain amount of water, step 2, crosslinking agent N, N'- methylene is added
Bisacrylamide, photoinitiator 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone, and uniform solution is stirred into, make third
The concentration of olefin(e) acid is 20%g/mL, and the quality of the nano cellulose crystal-g- polyacrylamide is the 0.005 of acrylic acid quality
~0.04 times, the quality of crosslinking agent is 0.0001~0.0005 times of acrylic acid quality, and the quality of photoinitiator is acrylic acid matter
0.02~0.04 times of amount；Then acquired solution is poured into container, makes 3~5mm of liquid level, and use wavelength for
The high-pressure sodium lamp that 365nm, power are 500~1000w is ultraviolet source, is gathered after 20~40min of photopolymerization at room temperature
Sodium acrylate/nano cellulose crystal composite high-water-absorptivresin resin is crossed 60 meshes by product drying obtained, after mechanical crushing and is obtained
To Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin.
2. a kind of Sodium Polyacrylate described in claim 1/nano cellulose crystal composite high-water-absorptivresin resin preparation method system
Standby Sodium Polyacrylate/nano cellulose crystal composite high-water-absorptivresin resin.
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| US4051086A (en) * | 1976-03-25 | 1977-09-27 | Hercules Incorporated | Absorption rate of absorbent polymers by treating with glyoxal |
| CA1221307A (en) * | 1982-12-02 | 1987-05-05 | Nobutaka Tani | Adsorbent and process for preparing the same |
| JPH0613586B2 (en) * | 1984-10-17 | 1994-02-23 | ダイセル化学工業株式会社 | High absorbent material |
| CN1315897C (en) * | 2004-06-29 | 2007-05-16 | 北京理工大学 | Process for preparing cellulose modified high water absorption resin |
| EP2440590B1 (en) * | 2009-06-09 | 2018-09-12 | William Chambers | Biodegradable absorbent material and method of manufacture |
| CN103214623B (en) * | 2013-05-11 | 2015-02-04 | 罗卫华 | Preparation method of surface-grafted modified nanocellulose crystal |
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