CN109485876A - A kind of preparation method of base catalysis PVA gel beads - Google Patents
A kind of preparation method of base catalysis PVA gel beads Download PDFInfo
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- CN109485876A CN109485876A CN201811340193.XA CN201811340193A CN109485876A CN 109485876 A CN109485876 A CN 109485876A CN 201811340193 A CN201811340193 A CN 201811340193A CN 109485876 A CN109485876 A CN 109485876A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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Abstract
The present invention relates to a kind of preparation methods of base catalysis PVA gel beads.This method with polyvinyl alcohol (PVA) be raw material, using NaOH as catalyst, to be saturated boric acid and CaCl2For crosslinking agent, reacts hydroxyl and boric acid molecule on PVA strand and generate ester bond, final tangle forms the PVA gel beads of diameter about 3mm.NaOH is catalyzed PVA first and realizes complete alcoholysis, and PVA long-chain molecule is unfolded, and is allowed to side chain full of active hydroxyl, is saturated boric acid and CaCl when instilling2After solution, the hydroxyl that NaOH can further be catalyzed PVA molecular side chain is chemically crosslinked with boric acid molecule by ester bond, PVA gel beads have water-swellable is low, mechanical strength is good, stabilization be not easy adhesion, it is provided simultaneously with that structure is uniform, biocompatibility is good, is easy to store, is suitable for the packing material of biofilm carrier in wastewater treatment bioreactor and high-speed upflow bioreactor.
Description
Technical field
The invention belongs to field of environment engineering, and in particular to a kind of preparation method of base catalysis PVA gel beads.
Background technique
Take polyvinyl alcohol (PVA) as the high molecular material of representative, is conducive to microorganism in waste water biological treatment reactor
Biofilm formation growth, so as to promote the quick start and high load capacity stable operation of reactor.
PVA is a kind of common one of water soluble polymer, contains a hydroxyl on strand on each repetitive unit
Base, since hydroxyl size is small, polarity is strong, therefore PVA has good water solubility, film forming, cohesion, is easy to hand over by hydrogen bond
Connection generates gel.PVA gel has the characteristics that water content is high, toxicity is low, good biocompatibility, defends in agricultural, biology, medical treatment
The fields such as life, environmental protection have wide application prospect.However, there are mechanicalness differences for the PVA gel formed by hydrogen bond self-crosslinking
Defect, to strongly limit its popularization and application.Largely studies have shown that can be by being physical crosslinking and being chemically crosslinked improvement
The mechanical strength of PVA gel rubber material.PVA physical crosslinking is strengthened using circulating freezing resistance method, intramolecular can be made to form hydrogen bond, crystallite area
And the crosslinking of macromolecular inter-chain entanglement, then three-dimensional net structure is formed by hydrophobic effect, although this method is to a certain extent
The problem of improving the mechanical strength of PVA gel, but being present in easy swelling fracture in water, so as to shorten its service life.
Using saturation boric acid and CaCl2For the chemical crosslink technique of chemical cross-linking agent, the intermolecular binding force of PVA can be reinforced by ester bond,
It is crosslinked the gel rubber material water resistance obtained and mechanical property significantly improves, so that its service life is extended, however this method is still
In the presence of halfway problem is crosslinked, the reactive group on unreacted PVA side chain makes the gel rubber material of preparation be easy to viscous mutually
Even reunite, and is unfavorable for stablizing for product and saves and apply.In recent years, these problems are surrounded, scholars attempt using different
Crosslinking agent (glutaraldehyde, epoxychloropropane etc.) improves PVA crosslinking, but obtain that mechanical strength is good, water-swellable is low and
The stable PVA gel rubber material for being not easy adhesion still belongs to blank.
Summary of the invention
It is an object of the invention to overcome the above deficiency, a kind of preparation method of base catalysis PVA gel beads, this method are provided
Water-swellable is low, mechanical strength is good, stabilization is not easy adhesion low cost, and it is equal to be provided simultaneously with structure by gel beads prepared by this method
Even, porous, nontoxic, density and moderate dimensions, biocompatibility are good, are easy to the advantages that storing, and it is raw to be suitable for wastewater treatment
The packing material of biofilm carrier in object reactor and high-speed upflow bioreactor.
The technical scheme of the present invention is realized as follows:
The preparation method of PVA gel beads under a kind of base catalysis, carries out in accordance with the following steps:
(1) PVA is dissolved in the water under water bath condition；
(2) NaOH is added in deionized water, stirs evenly the catalyst as cross-linking reaction；
(3) with prepared NaOH catalyst dilution PVA solution, mechanical stirring is mixed, and ultrasound removes bubble, and it is solidifying to form homogeneous
Glue；
(4) CaCl is added in saturation boric acid solution2, stir evenly as chemical cross-linking agent.
(5) above-mentioned homogeneous gel raw material is instilled in churned mechanically chemical cross-linking agent by syringe and is handed over
Connection forms milky, bright, and diameter is the PVA gel beads of 2mm~3mm；
(7) the PVA gel beads are washed with deionized for several times, are stored in distilled water.
PVA mass used is 10-12g in step (1), and bath temperature is 80~90 DEG C, and water bath time is 50~60min；
NaOH catalyst used is that 4~6gNaOH is added in 100mL water in step (2)；
It is 8%~10% that NaOH catalyst dilution PVA solution to mass fraction is used in step (3).
Chemical cross-linking agent is to be saturated the CaCl of 1~2g of addition in boric acid in 100~120mL in step (4)2, stir evenly.
The chemical crosslinking time is 4min~3h in step (4).
The beneficial effects of the present invention are as follows: the gel beads preparation process that (1) is invented is simple, raw material are cheap and easy to get, are suitble to
Large-scale industrial production is carried out, biological wastewater treatment field can be applied to, have excellent economy and environmental benefit.(2)
The present invention solves the problems, such as that pure PVA is difficult to be crosslinked in traditional cross-linking process, reduces preparation cost；Obtained PVA gel beads
Pore structure is uniform, water-tolerant, stable mechanical property, and water-soluble expansion does not occur, and service life is longer, can be filled in biological anti-
It answers in device, promotion forms good granule sludge, and reactor plugs failure caused by can preventing because of sludge loss occurs；
Specific embodiment
With specific embodiment, the present invention will be further described below.
The preparation method of PVA gel beads, successively comprises the steps of: under a kind of base catalysis of embodiment 1
1) preparation raw material solution: weighing 12g polyvinyl alcohol with electronic balance and be dissolved in 100mL distilled water, under 90 DEG C of water-baths
Mechanical stirring 60min obtains the PVA solution that mass fraction is 12% to being completely dissolved.
2) prepare NaOH catalyst: every 100mL solution adds 6gNaOH, stirs evenly.
3) with NaOH catalyst dilution PVA solution: taking the NaOH solution in 15mL step 2), be added to the 12% of 50ml
In PVA solution, after being diluted mass fraction be 9.8% PVA solution.
3) prepare chemical cross-linking agent: 120mL is saturated in boric acid plus 2gCaCl2, stir evenly.
4) PVA gel beads are prepared: the PVA gel solution after above-mentioned dilution uniformly being instilled into chemical cross-linking agent using syringe
In, it keeps stirring.The gel is continued to be placed in and solidifies 4min in chemical cross-linking agent to settling, takes out, is washed with distilled water
It is in neutrality for several times to pH.Milky is obtained, diameter is~3mm, and the PVA gel beads that elasticity is good cut and visually observe the gel beads
For uniform gel structure.
The preparation method of PVA gel beads, successively comprises the steps of: under a kind of base catalysis of embodiment 2
1) preparation raw material solution: weighing 10g polyvinyl alcohol with electronic balance and be dissolved in 100mL distilled water, under 80 DEG C of water-baths
Mechanical stirring 30min obtains the PVA solution that mass fraction is 10% to being completely dissolved.
2) prepare NaOH catalyst: every 100mL solution adds 4gNaOH, stirs evenly.
3) with NaOH catalyst dilution PVA solution: taking the NaOH solution in 15mL step 2), be added to the 10% of 50ml
In PVA solution, after being diluted mass fraction be 8.8% PVA solution.
3) prepare chemical cross-linking agent: 100mL is saturated in boric acid plus 1gCaCl2, stir evenly.
4) PVA gel beads are prepared: the PVA gel solution after above-mentioned dilution uniformly being instilled into chemical cross-linking agent using syringe
In, it keeps stirring.The gel is continued to be placed in and solidifies 1h in chemical cross-linking agent to settling, takes out, is washed with distilled water number
It is secondary to be in neutrality to pH.Milky is obtained, diameter is~3mm, and the PVA gel beads that elasticity is good cut and visually observe the gel beads table
Face forms shell-like structure, but the shell-like structure is not peeling-off with internal structure, is completely embedded, the surface of gel and internal void
Structure is flourishing.
Embodiment 3: the preparation method of PVA gel beads under a kind of base catalysis successively comprises the steps of:
1) preparation raw material solution: weighing 10g polyvinyl alcohol with electronic balance and be dissolved in 100mL distilled water, under 80 DEG C of water-baths
Mechanical stirring 30min obtains the PVA solution that mass fraction is 10% to being completely dissolved.
2) prepare NaOH catalyst: every 100mL solution adds 4gNaOH, stirs evenly.
3) with NaOH catalyst dilution PVA solution: taking the NaOH solution in 15mL step 2), be added to the 10% of 50ml
In PVA solution, after being diluted mass fraction be 8.8% PVA solution.
3) prepare chemical cross-linking agent: 100mL is saturated in boric acid plus 1gCaCl2, stir evenly.
4) PVA esterification gel beads are prepared: the PVA gel solution after above-mentioned dilution uniformly being instilled into chemistry friendship using syringe
Join in agent, keeps stirring.The gel is continued to be placed in and solidifies 3h in chemical cross-linking agent to settling, takes out, is washed with distillation
It washs and is in neutrality for several times to pH.Milky is obtained, diameter is~3mm, and the PVA gel beads that elasticity is good cut and visually observe the gel
Bead surface forms shell-like structure, and the shell-like structure is peeling-off with internal structure, is not connected to, the surface of gel and internal void knot
Structure is flourishing.
Settling property is good in water for the PVA gel beads being prepared, diameter 2mm~3mm, continuous mechanical stirring do not dissolve out,
It does not rupture, elasticity is good, stable mechanical performance, and the gel beads are brighter as the extension of chemical crosslinking time forms shell structurre
It is aobvious, to 3h after shell structurre inside the gel beads be completely exfoliated, form the structure of " valve jacket ball ", the surface shell of the gel and
Internal holes sphere is provided with flourishing pore structure.
Embodiment 4: Performance Evaluation of the PVA gel beads as water process anaerobic organism carrier under base catalysis
The prepared PVA gel beads of investment in the USAB (upflow type anaerobic reactor) that laboratory is currently running, should
Seed sludge is anaerobic ammonium oxidation sludge in UASB, and with the operation of reactor, after cultivating 10d, the PVA gel beads structure is complete
Whole, color is converted into bronzing by milky, does not rupture.SEM (scanning electron microscope) is the result shows that anaerobism ammonia oxygen in the PVA gel beads
Metaplasia object apposition growth is in good condition, it was demonstrated that the PVA gel beads have good biocompatibility, can be used in anaerobic grain
The fast culture of sludge.
Solves simple physical or simple in the way of the crosslinking proposed by the present invention for carrying out gelation by PVA under base catalysis
The drawbacks of being chemically crosslinked gel beads.And the catalytic action of NaOH makes the esterification of PVA and boric acid more thorough, to keep away
Exempt from residual activity group and water on PVA and forms the water-soluble expansion of hydrogen bond bring.Ca2+And Na+Residual in the gel beads mentions
The high intensity and permeability of gel.The preparation method operating process is easy, is conducive to expanding production, and gel beads synthesized
Material is nontoxic after raw material involved in journey and synthesis, has good environmental safety.The more importantly gel
Strain is provided with porous structure, and good biocompatibility is conducive to attached growth of microorganisms.Preparation method proposed by the present invention can be prepared
Stable mechanical performance out, water resistant power performance of flushing is strong, the gel beads of size and medium density, is suitable for being filled in general biological respinse
Device and high-speed upflow bioreactor carry out microculture.
In conclusion the present invention is solidifying by the PVA that the preparation method that PVA under base catalysis and boric acid in-situ chemical are crosslinked obtains
Glue bead is novel ideal biomaterial.The gel beads have both good bioaffinity and chemical stability, more presently commercially available
Biomaterial more meet the needs of environmental science.The present invention prepare gel beads raw material sources are extensive and nontoxic nothing
Evil, at low cost, preparation process is simple, prepares, securely and reliably, environmental benefit with higher and economic results in society under normal pressure.
Claims (6)
1. a kind of preparation method of base catalysis PVA gel beads, which is characterized in that carry out in accordance with the following steps:
(1) PVA is dissolved in the water under water bath condition；
(2) NaOH is added in deionized water, stirs evenly the catalyst as cross-linking reaction；
(3) with prepared NaOH catalyst dilution PVA solution, mechanical stirring is mixed, and ultrasound removes bubble, forms homogeneous gel；
(4) CaCl is added in saturation boric acid solution2, stir evenly as chemical cross-linking agent；
(5) above-mentioned homogeneous gel raw material is instilled in churned mechanically chemical cross-linking agent by syringe and is crosslinked, shape
Bright at milky, diameter is the PVA gel beads of 2mm~3mm；
(7) the PVA gel beads are washed with deionized for several times, are stored in distilled water.
2. a kind of preparation method of base catalysis PVA gel beads according to claim 1, which is characterized in that used in step (1)
PVA mass is 10-12g, and bath temperature is 80~90 DEG C, and water bath time is 50~60min.
3. a kind of preparation method of base catalysis PVA gel beads according to claim 1, which is characterized in that used in step (2)
NaOH catalyst is that 4~6gNaOH is added in 100mL water.
4. a kind of preparation method of base catalysis PVA gel beads according to claim 1, which is characterized in that used in step (3)
NaOH catalyst dilution PVA solution to mass fraction is 8%~10%.
5. a kind of preparation method of base catalysis PVA gel beads according to claim 1, which is characterized in that chemical in step (4)
Crosslinking agent is to be saturated the CaCl of 1~2g of addition in boric acid in 100~120mL2, stir evenly.
6. a kind of preparation method of base catalysis PVA gel beads according to claim 1, which is characterized in that chemical in step (4)
Crosslinking time is 4min~3h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110496607A (en) * | 2019-07-31 | 2019-11-26 | 西安交通大学 | A kind of preparation method of the immobilized powders calcium silicate CSH gel beads of dephosphorization adsorbent PVA |
| CN110743514A (en) * | 2019-11-22 | 2020-02-04 | 西安交通大学 | Preparation method of dye adsorbent PVA/ZSM-5 gel beads |
| CN110790885A (en) * | 2019-08-30 | 2020-02-14 | 武汉理工大学 | Polyvinyl alcohol/chitosan quaternary ammonium salt antibacterial self-healing hydrogel and preparation method and application thereof |
| CN111115795A (en) * | 2020-01-14 | 2020-05-08 | 丽水学院 | Ion response biofilm formation material for sewage treatment and preparation method thereof |
| CN112159538A (en) * | 2020-09-10 | 2021-01-01 | 北京化工大学常州先进材料研究院 | Catalyst-supported polyvinyl alcohol vortex ring derivative particle |
| CN114044925A (en) * | 2021-12-06 | 2022-02-15 | 西安交通大学 | Preparation method and application of polyvinyl alcohol gel material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110496607A (en) * | 2019-07-31 | 2019-11-26 | 西安交通大学 | A kind of preparation method of the immobilized powders calcium silicate CSH gel beads of dephosphorization adsorbent PVA |
| CN110496607B (en) * | 2019-07-31 | 2020-10-27 | 西安交通大学 | Preparation method of phosphorus removal adsorbent PVA (polyvinyl alcohol) immobilized powder calcium silicate CSH (calcium silicate chloride) gel beads |
| CN110790885A (en) * | 2019-08-30 | 2020-02-14 | 武汉理工大学 | Polyvinyl alcohol/chitosan quaternary ammonium salt antibacterial self-healing hydrogel and preparation method and application thereof |
| CN110790885B (en) * | 2019-08-30 | 2022-05-03 | 武汉理工大学 | Polyvinyl alcohol/chitosan quaternary ammonium salt antibacterial self-healing hydrogel and preparation method and application thereof |
| CN110743514A (en) * | 2019-11-22 | 2020-02-04 | 西安交通大学 | Preparation method of dye adsorbent PVA/ZSM-5 gel beads |
| CN110743514B (en) * | 2019-11-22 | 2020-07-28 | 西安交通大学 | Preparation method of dye adsorbent PVA/ZSM-5 gel beads |
| CN111115795A (en) * | 2020-01-14 | 2020-05-08 | 丽水学院 | Ion response biofilm formation material for sewage treatment and preparation method thereof |
| CN112159538A (en) * | 2020-09-10 | 2021-01-01 | 北京化工大学常州先进材料研究院 | Catalyst-supported polyvinyl alcohol vortex ring derivative particle |
| CN112159538B (en) * | 2020-09-10 | 2023-04-14 | 北京化工大学常州先进材料研究院 | Catalyst-supported polyvinyl alcohol vortex ring derivative particle |
| CN114044925A (en) * | 2021-12-06 | 2022-02-15 | 西安交通大学 | Preparation method and application of polyvinyl alcohol gel material |
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