CN109821516A - A kind of preparation method of carboxymethyl chitosan modified polyurethane foam - Google Patents
A kind of preparation method of carboxymethyl chitosan modified polyurethane foam Download PDFInfo
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- CN109821516A CN109821516A CN201910260703.0A CN201910260703A CN109821516A CN 109821516 A CN109821516 A CN 109821516A CN 201910260703 A CN201910260703 A CN 201910260703A CN 109821516 A CN109821516 A CN 109821516A
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- carboxymethyl chitosan
- polyurethane foam
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Abstract
The present invention relates to adsorption and separation material preparation technical fields, and in particular to a kind of preparation method of carboxymethyl chitosan modified polyurethane foam.The invention solves the difficult problems of easy aggregation of the existing technology and separation, in order to reach the purpose of the present invention, present invention provide the technical scheme that carrying out polyurethane prepolymer and carboxymethyl chitosan solution in a kettle to be vigorously stirred mixing first；Then mixed solution is dried at room temperature for obtaining carboxymethyl chitosan modified polyurethane foam, is washed with deionized, dried.Prepared composite foam shows high adsorption and good recuperability, and has good mechanical performance and stability.
Description
Technical field
The present invention relates to adsorption and separation material preparation technical fields, and in particular to a kind of carboxymethyl chitosan modified polyurethane
The preparation method of foam.
Background technique
Biological adsorption have many advantages, such as in terms of wastewater treatment high efficiency, it is easy to operate, reusable, inexpensive and by
Extensive concern.Many biomaterials have high metal binding ability and highly selective biological adsorption agent for developing.Wherein,
Chitosan and its derivative is resourceful, renewable, and the presence of the functional group on polymer chain such as hydroxyl, amino, acetyl group makes
It is easy to chemical modification, is the biological adsorption agent of function admirable.Carboxymethyl chitosan is that chitosan obtains after carboxymethylation reaction
The analog derivative arrived, the introducing of carboxyl make it combine metal ion and greatly improve with reactive dye ability.But carboxymethyl shell
Glycan there is a problem that easily assembling and separating hardly possible when carrying out wastewater treatment.
A kind of practical approach solved these problems is that carboxymethyl chitosan is embedded in polymer substrate, so that adsorbent
It can freely interact with metal ion or reactive dye and be easy to separate with sewage.Li Wei et al. consolidates active carbon
It is scheduled in polyurethane foam for adsorbing phenol, iodine and methylene blue.Sung Wook Won et al. polyurethane fixes glutamic acid rod
Bacillus is used for adsorption activity Huang 2, et al. attapulgite be fixed in polyurethane foam be used for malachite green (MG) waste water from dyestuff
Processing.
Summary of the invention
The present invention provides a kind of preparation methods of carboxymethyl chitosan modified polyurethane foam, efficiently solve existing skill
The difficult problem of easy aggregation, the separation that art is faced in adsorption process.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of carboxymethyl chitosan modified polyurethane foam, comprising the following steps:
Step 1: being dissolved in the carboxymethyl chitosan solution that configuration quality score is 1 ~ 4% in deionized water for carboxymethyl chitosan,
Then MDI or TDI polyurethane prepolymer and carboxymethyl chitosan solution 1:1 in mass ratio ~ 3 are added in reaction kettle, 10 ~ 40
At DEG C, it is vigorously stirred 30 ~ 60s of mixing, obtains mixed solution；
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains carboxymethyl chitosan after being dried at room temperature for 10 ~ 30min
CMCTS-PU foam in pallet is washed with deionized 4 ~ 6 times sugared modified polyurethane foam, 8 in 50 ~ 70 DEG C of baking ovens ~
12 h。
Further, in the step 1, carboxymethyl chitosan degree of substitution >=80%.
Further, in the step 1, polyurethane prepolymer is TDI performed polymer or the MDI pre-polymerization of terminal isocyanate group
Body.
Compared with prior art, the invention has the advantages that
1, it when present invention preparation CMCTS-PU foam, is prepared according to gradually addition polymerization principle, does not use solvent and catalyst, tool
There are environment friendly, nontoxic, easily biological-degradable.
2, biomass resource is rationally utilized in the present invention, and carboxymethyl chitosan is inhaled as heavy metal ion and the dye of positive ion
Attached dose, carrier of the polyurethane foam as absorption, the composite material synthesized can be used as the suction of metal ion and the dye of positive ion
It is attached, there is high biological degradability, antibiotic property.
3, CMCTS-PU foam produced by the present invention has the porous structure of high-specific surface area, is guaranteeing high adsorption and can
Under the premise of recyclability, while the mechanical strength and stability of product are improved, to Cu2+、Cd2+、Pb2+Maximum adsorption capacity point
Not Wei 75.8 mg/g, 97 mg/g, 209.3 mg/g, be 118 mg/g to the maximum adsorption capacity of methylene blue.
4, applied widely: to can be widely applied to metal ion (Cu2+, Cd2+And Pb2+) with the absorption of the dye of positive ion.
Detailed description of the invention
Fig. 1 is the infrared comparison diagram of a kind of CMCTS-PU foam and pure PU foamed material；
Fig. 2 is that a kind of SEM of CMCTS-PU foam schemes.
Specific embodiment
The present invention is described in further details combined with specific embodiments below.
A kind of preparation method of carboxymethyl chitosan modified polyurethane foam, comprising the following steps:
Step 1: being dissolved in the carboxymethyl chitosan solution that configuration quality score is 1 ~ 4% in deionized water for carboxymethyl chitosan,
Then MDI or TDI polyurethane prepolymer and carboxymethyl chitosan solution 1:1 in mass ratio ~ 3 are added in reaction kettle, 10 ~ 40
At DEG C, it is vigorously stirred 30 ~ 60s of mixing, obtains mixed solution；
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains carboxymethyl chitosan after being dried at room temperature for 10 ~ 30min
CMCTS-PU foam in pallet is washed with deionized 4 ~ 6 times sugared modified polyurethane foam, 8 in 50 ~ 70 DEG C of baking ovens ~
12 h。
In step 1, carboxymethyl chitosan degree of substitution >=80%.
In step 1, polyurethane prepolymer is the TDI performed polymer or MDI performed polymer of terminal isocyanate group.
The reaction equation of above-mentioned preparation method is as follows:
Selected carboxymethyl chitosan degree of substitution >=80% in embodiment.
In use, CMCTS-PU foam is cut into about 0.3g bulk, it is put into conical flask, 50 mL initial concentrations, which are added, is
(heavy metal solution pH is maintained between 5 ~ 6 to prevent heavy metal heavy for 100 mg/L heavy metal solutions or dye of positive ion solution
It forms sediment).Bottleneck is sealed with preservative film, is placed in constant temperature oscillator, 12 ~ 24 h of oscillation absorption under the conditions of 10 ~ 40 DEG C.
Regeneration method: the CMCTS-PU foam after using is immersed in 6 ~ 8 h in the HCl solution of 0.1mol/L, then uses
Deionized water wash 4 ~ 6 times after in 50 ~ 70 DEG C of baking ovens 8 ~ 12 h, obtain regenerated CMCTS-PU foam.
Embodiment 1
Step 1: carboxymethyl chitosan is dissolved in the carboxymethyl chitosan solution that configuration quality score is 2% in deionized water, so
10 g MDI polyurethane prepolymers and 10 g carboxymethyl chitosan solutions 1:1 in mass ratio are added in reaction kettle afterwards, at 10 DEG C
Under, it is vigorously mixed 60s using mechanical agitator, obtains mixed solution.
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains CMCTS-PU bubble after being dried at room temperature for 10min
CMCTS-PU foam in pallet is washed with deionized 4 times foam, dries 10 h in 50 DEG C of baking ovens.
In use, CMCTS-PU foam is cut into about 0.3 g bulk, it is put into conical flask, the initial Cu of 50 mL is added2+It is dense
Degree is 100 mg/L Cu2+Solution, Cu2+PH value of solution maintains 5 to prevent its precipitating.Bottleneck is sealed with preservative film, is placed in constant temperature
In oscillator, 24 h of oscillation absorption under the conditions of 10 DEG C.
Regeneration method: Cu will be adsorbed2+CMCTS-PU foam be immersed in 6 h in the HCl solution of 0.1mol/L, then use
Deionized water wash 4 times after in 50 DEG C of baking ovens 10 h, obtain regenerated CMCTS-PU foam.
Embodiment 2
Step 1: carboxymethyl chitosan is dissolved in the carboxymethyl chitosan solution that configuration quality score is 2% in deionized water, so
10 g MDI polyurethane prepolymers and 20 g carboxymethyl chitosan solutions 1:2 in mass ratio are added in reaction kettle afterwards, at 20 DEG C
Under, 50 s are vigorously mixed using mechanical agitator, obtain mixed solution.
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains CMCTS-PU bubble after being dried at room temperature for 20min
CMCTS-PU foam in pallet is washed with deionized 4 times foam, dries 12 h in 60 DEG C of baking ovens.
In use, CMCTS-PU foam is cut into about 0.3 g bulk, it is put into conical flask, the initial Cd of 50 mL is added2+It is dense
Degree is 100 mg/L Cd2+Solution, Cd2+PH value of solution maintains 5 to prevent its precipitating.Bottleneck is sealed with preservative film, is placed in constant temperature
In oscillator, 12 h of oscillation absorption under the conditions of 20 DEG C.
Regeneration method: Cd will be adsorbed2+CMCTS-PU foam be immersed in 7 h in the HCl solution of 0.1mol/L, then use
Deionized water wash 5 times after in 60 DEG C of baking ovens 12 h, obtain regenerated CMCTS-PU foam.
Embodiment 3
Step 1: carboxymethyl chitosan is dissolved in the carboxymethyl chitosan solution that configuration quality score is 2% in deionized water, so
10 g TDI polyurethane prepolymers and 30 g carboxymethyl chitosan solutions 1:3 in mass ratio are added in reaction kettle afterwards, at 25 DEG C
Under, 60 s are vigorously mixed using mechanical agitator, obtain mixed solution.
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains CMCTS-PU bubble after being dried at room temperature for 30min
CMCTS-PU foam in pallet is washed with deionized 6 times foam, dries 8 h in 70 DEG C of baking ovens.
In use, CMCTS-PU foam is cut into about 0.3 g bulk, it is put into conical flask, the initial methylene of 50 mL is added
Blue concentration is the solution of 100 mg/L.Bottleneck is sealed with preservative film, is placed in constant temperature oscillator, absorption is vibrated under the conditions of 30 DEG C
16 h。
Regeneration method: being immersed in 8 h in the HCl solution of 0.1mol/L for the CMCTS-PU foam for adsorbing methylene blue,
Then after being washed with deionized 6 times in 70 DEG C of baking ovens 8 h, obtain regenerated CMCTS-PU foam.
Above-described embodiment 3 is most preferred embodiment, and synthesized CMCTS-PU foam cell is uniform, surface area is big.Absorption speed
Rate is fast, and adsorption effect is good.
Referring to Fig. 1, Fig. 1 is the infrared spectrogram of pure PU and CMCTS-PU.It can be seen from the infrared spectrum of PU
3310cm-1、1652cm-1And 1537cm-1Place is respectively N-H, CO-NH and NH2Vibration absorption peak, illustrate reaction generate ammonia
Carbamate base.1610cm-1And 830cm-1Place is the skeletal vibration and out-of-plane bending vibration of phenyl ring.2760cm-1、1710cm-1With
1222cm-1Correspond respectively to the O-H stretching vibration, C ═ O stretching vibration and C-O stretching vibration of carboxyl in CMCTS-PU.Although PU
It is identical with most of absorption peaks of CMCNS-PU, but CMCTS-PU is due to the strong influence by intermolecular hydrogen bonding, 3365
cm-1The stretching vibration absworption peak intensity for locating O-H is higher than the absorption peak of PU.
Referring to fig. 2, Fig. 2 is the SEM figure of PU and CMCTS-PU.It can be seen that the cell size of PU is more uniform from Fig. 2 a,
The smooth densification of hole surface.And the cell size of CMCTS-PU is uneven in Fig. 2 b, there is obvious fold on surface.Compared with PU, CMCTS-
The aperture of PU is smaller, and quantity is more, this illustrates that CMCTS-PU has bigger surface area and more ion channels.This may be
Because CMCTS reacts the site for increasing abscess and being formed with PPU's, to produce more porous knot in abscess forming process
Structure.
Claims (3)
1. a kind of preparation method of carboxymethyl chitosan modified polyurethane foam, which comprises the following steps:
Step 1: being dissolved in the carboxymethyl chitosan solution that configuration quality score is 1 ~ 4% in deionized water for carboxymethyl chitosan,
Then MDI or TDI polyurethane prepolymer and carboxymethyl chitosan solution 1:1 in mass ratio ~ 3 are added in reaction kettle, 10 ~ 40
At DEG C, it is vigorously stirred 30 ~ 60s of mixing, obtains mixed solution；
Step 2: above-mentioned mixed solution is poured into pallet rapidly, obtains carboxymethyl chitosan after being dried at room temperature for 10 ~ 30min
CMCTS-PU foam in pallet is washed with deionized 4 ~ 6 times sugared modified polyurethane foam, 8 in 50 ~ 70 DEG C of baking ovens ~
12 h。
2. a kind of preparation method of carboxymethyl chitosan modified polyurethane foam according to claim 1, which is characterized in that
In the step 1, carboxymethyl chitosan degree of substitution >=80%.
3. a kind of preparation method of carboxymethyl chitosan modified polyurethane foam according to claim 1 or claim 2, feature exist
In in the step 1, polyurethane prepolymer is the TDI performed polymer or MDI performed polymer of terminal isocyanate group.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115715975A (en) * | 2022-10-28 | 2023-02-28 | 佳化化学科技发展（上海）有限公司 | Porous spherical adsorbent and preparation method and application thereof |
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| CN115715975A (en) * | 2022-10-28 | 2023-02-28 | 佳化化学科技发展（上海）有限公司 | Porous spherical adsorbent and preparation method and application thereof |
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