CN113265068B - Method for dissolving polyvinyl alcohol with high alcoholysis degree - Google Patents

Method for dissolving polyvinyl alcohol with high alcoholysis degree Download PDF

Info

Publication number
CN113265068B
CN113265068B CN202110577614.6A CN202110577614A CN113265068B CN 113265068 B CN113265068 B CN 113265068B CN 202110577614 A CN202110577614 A CN 202110577614A CN 113265068 B CN113265068 B CN 113265068B
Authority
CN
China
Prior art keywords
polyvinyl alcohol
ion
mol
dissolving
alcoholysis degree
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110577614.6A
Other languages
Chinese (zh)
Other versions
CN113265068A (en
Inventor
郭辉
李平
肖雪梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Yat Sen University
Original Assignee
Sun Yat Sen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sun Yat Sen University filed Critical Sun Yat Sen University
Priority to CN202110577614.6A priority Critical patent/CN113265068B/en
Publication of CN113265068A publication Critical patent/CN113265068A/en
Application granted granted Critical
Publication of CN113265068B publication Critical patent/CN113265068B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • 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
    • 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
    • C08K3/16—Halogen-containing compounds
    • C08K2003/168—Zinc halides
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K3/16—Halogen-containing compounds
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The application belongs to the technical field of dissolving polyvinyl alcohol, and particularly relates to a method for dissolving polyvinyl alcohol with high alcoholysis degree. The application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps: mixing and dissolving polyvinyl alcohol, small molecular additives and water to obtain dissolved polyvinyl alcohol; the alcoholysis degree of the polyvinyl alcohol is more than or equal to 95% mol/mol; small molecule additives ionize anions and cations in water; the anion is selected from fluoride ion, chloride ion, bromide ion, iodide ion, nitrate radical, carbonate radical, hypochlorite radical or sulfate radical, etc.; the cation is selected from potassium ion, sodium ion, lithium ion, cesium ion, calcium ion, magnesium ion, aluminum ion, iron ion, ferrous ion, ammonium ion, hydrogen ion, cobalt ion, etc. The method can effectively solve the technical problems of high energy consumption, time and labor waste and easy occurrence of safety accidents in the existing method for dissolving the polyvinyl alcohol with high alcoholysis degree in a high-temperature environment.

Description

Method for dissolving polyvinyl alcohol with high alcoholysis degree
Technical Field
The application belongs to the technical field of dissolving polyvinyl alcohol, and particularly relates to a method for dissolving polyvinyl alcohol with high alcoholysis degree.
Background
The structure of polyvinyl alcohol (PVA) is closely related to its properties. Among them, the degree of alcoholysis of PVA is an important parameter affecting its use. Depending on the degree of alcoholysis of polyvinyl acetate, the currently available polyvinyl alcohols can be classified into the following two main categories: fully alcoholyzed (> 99%) and partially alcoholyzed (78-90%). Compared with the PVA with low alcoholysis degree, the PVA with high alcoholysis degree has good mechanical properties, film-forming properties and the like, and has wider application prospect in daily life of people. Unlike the partially alcoholysis type PVA, the fully alcoholysis type PVA has high crystallinity, and a large amount of hydroxyl groups on the side chains of the polymer causes strong interaction force between molecules, so that the PVA is difficult to dissolve in water at normal temperature. Therefore, the industry generally requires a long period of high temperature heating to ensure complete dissolution of the PVA. This method consumes a large amount of energy and at the same time brings about a certain degree of danger. In the application of PVA, the polyvinyl alcohol product is generally dissolved in a solvent, and then converted into a solution form for further application in various fields. Therefore, the dissolution process of the PVA polymer with high alcoholysis degree is a key technical problem which restricts the application of the PVA polymer.
Therefore, the existing general method for dissolving PVA with high alcoholysis degree is to heat the PVA for several hours at a high temperature of between 90 and 100 ℃ for dissolving the PVA. The process has the advantages of single dissolving mode, complex operation and time consumption, high-temperature heating usually has higher requirements on production equipment, and the production process not only has large energy consumption but also is easy to cause safety accidents. Therefore, the PVA material with high alcoholysis degree at normal temperature can be dissolved, so that the problems of high energy consumption and the like in industrial production can be solved, and meanwhile, some dangerous problems can be avoided.
Disclosure of Invention
In view of this, the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which can effectively solve the technical problems of high energy consumption, time and labor waste and easy occurrence of safety accidents in the existing method for dissolving PVA with high alcoholysis degree in high-temperature environment.
The application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, small molecular additives and water to obtain dissolved polyvinyl alcohol;
wherein the alcoholysis degree of the polyvinyl alcohol is greater than or equal to 95% mol/mol;
the small molecule additive ionizes anions and cations in water; the anion is selected from one or more of fluoride, chloride, bromide, iodide, nitrate, nitrite, carbonate, bicarbonate, hypochlorite, sulfate, bisulfate, sulfite, bisulfite, thiocyanate, formate and acetate; the cation is selected from one or more of potassium ion, sodium ion, lithium ion, cesium ion, calcium ion, magnesium ion, aluminum ion, iron ion, ferrous ion, copper ion, titanium ion, ammonium ion, hydrogen ion, nickel ion, cobalt ion, zinc ion, molybdenum ion and manganese ion.
In another embodiment, the small molecule additive may be one small molecule salt, may be one small molecule acid, may be multiple small molecule salts, and may be a mixture of the small molecule salt and the small molecule acid.
In another embodiment, the small molecule additive is selected from one or more of lithium chloride, magnesium nitrate, ferric nitrate, lithium iodide, potassium iodide, manganese chloride, zinc chloride, nitric acid, hydrochloric acid, cesium sulfate, ferrous chloride, potassium carbonate, ferrous ammonium sulfate, ferric iodide, formic acid, potassium thiocyanate, sodium bisulfite, and aluminum bromide.
In another embodiment, the final concentration of the small molecule additive is 0.3-15 mol/L.
In another embodiment, the final concentration of the small molecule additive is 1-12 mol/L.
In another embodiment, the addition amount of the polyvinyl alcohol in the dissolution system is 2-25% wt/wt.
In another embodiment, the addition amount of the polyvinyl alcohol in a dissolving system is 4-15% wt/wt.
In another embodiment, the polyvinyl alcohol is selected from one or more of PVA-1799, PVA-0599 and PVA-2899 types.
In another embodiment, the temperature of the mixing and dissolving is 0-50 ℃.
In another embodiment, the mixing and dissolving time is 1-60 min.
In another embodiment, the method for dissolving polyvinyl alcohol with high alcoholysis degree further comprises recovering the small molecule additive;
and recovering the small molecular additive from the dissolved polyvinyl alcohol by a wet spinning method, a direct dialysis method, heating recovery, a post-extension film-forming swelling method or a post-crosslinking water exchange method.
The micromolecular additive aqueous solution in the method can be recycled by a wet spinning method, a direct dialysis method, a flow-extending film-forming method or a water exchange method after crosslinking, accords with the green chemical concept, and realizes energy conservation and emission reduction.
According to the method, intermolecular interaction in a polyvinyl alcohol crystallization region is destroyed by using a small-molecule additive aqueous solution, and a method for efficiently dissolving polyvinyl alcohol with high alcoholysis degree at room temperature is developed. The method has the advantages of simple operation process, low energy consumption, low danger and low requirement on equipment. Meanwhile, the micromolecule additive can be recycled, so that the method has the advantages of safety and economy, the problems of high energy consumption and danger in high-temperature dissolution are solved, the dissolution method is short in time consumption, the properties of the obtained dissolved polyvinyl alcohol and the properties of the traditional high-temperature dissolved polyvinyl alcohol are basically not different, and the normal use in various fields is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a graph showing the appearance of the dissolution of a high alcoholysis degree polyvinyl alcohol at different times as provided in example 1 and comparative example 1 of the present application.
Detailed Description
The application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which is used for solving the technical defects of high energy consumption, time and labor waste and easy occurrence of safety accidents in the method for dissolving PVA with high alcoholysis degree in a high-temperature environment in the prior art.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The raw materials and reagents used in the following examples are commercially available or self-made.
Example 1
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, lithium chloride and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-1799 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 10.0 percent by weight/wt; the molar concentration of lithium chloride was 4M. Referring to fig. 1, fig. 1 is an appearance diagram of the dissolution of the polyvinyl alcohol with high alcoholysis degree at different times provided in the present application, example 1 and comparative example 1, wherein fig. 1 is an appearance diagram of the dissolution of the polyvinyl alcohol with high alcoholysis degree in example 1 after mixing time t ═ 0min and t ═ 5 min. As can be seen from FIG. 1, the polyvinyl alcohol of this example was completely dissolved after 5min at room temperature.
And (3) recovering lithium chloride by dialyzing the dissolved polyvinyl alcohol in pure water, so as to realize recycling.
Comparative example 1
The comparative example of the application provides a contrast dissolution method, and the specific method comprises the following steps:
referring to the process of example 1, except that no lithium chloride is added, polyvinyl alcohol is mixed and dissolved by pure water, and the rest of the process is identical to the process of example 1, as a result, referring to fig. 1, fig. 1 is an appearance diagram of the dissolution of polyvinyl alcohol with high alcoholysis degree at different times provided by the present application of example 1 and comparative example 1, wherein, at the right of fig. 1, the appearance diagram of the dissolution of polyvinyl alcohol with high alcoholysis degree of comparative example 1 after mixing time t ═ 0min and t ═ 5min is shown. As can be seen from FIG. 1, the polyvinyl alcohol of this comparative example was not soluble at room temperature.
Example 2
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, magnesium nitrate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 15.0 percent by weight/wt; the molar concentration of the magnesium nitrate is 1 mol/L. The polyvinyl alcohol of the example is completely dissolved after 30min at room temperature.
And recovering the additive from the dissolved polyvinyl alcohol by adopting a wet spinning method, thereby realizing recycling.
Example 3
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, ferric nitrate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-1797 type, and the alcoholysis degree is as follows: 97% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 9.0 percent by weight/wt; the molar concentration of the ferric nitrate is 12 mol/L. The polyvinyl alcohol of the embodiment is completely dissolved after 3min at 40 ℃.
The dissolved polyvinyl alcohol is swelled after being chemically crosslinked into gel, and the additive is recovered to realize recycling.
Example 4
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, potassium iodide and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-2899 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 6.5 percent by weight/wt; the molar concentration of potassium iodide was 6 mol/L. The polyvinyl alcohol of this example was completely dissolved after 15min at room temperature.
And (3) adopting a method of swelling after drying and film forming to the dissolved polyvinyl alcohol, recovering the additive, and realizing recycling.
Example 5
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, manganese chloride and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 9.2 percent by weight/wt; the molar concentration of the manganese chloride is 2 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 10min at 10 ℃.
Example 6
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, zinc chloride and pure water at room temperature to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 13.8 percent by weight/wt; the molar concentration of the zinc chloride is 2 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 20min at 50 ℃.
Example 7
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, nitric acid and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 8.2 percent by weight/wt; the molar concentration of the nitric acid is 2 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 15min at 30 ℃.
And (3) recovering the additive from the dissolved polyvinyl alcohol by adopting a heating and drying method, so as to realize recycling.
Example 8
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, cesium sulfate, ferrous chloride and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 12.1 percent by weight/wt; the total molar concentration of cesium sulfate and ferrous chloride was 2mol/L (molar ratio of cesium sulfate to ferrous chloride was 1: 1). In the case of the polyvinyl alcohol of this example, the polyvinyl alcohol was completely dissolved within 10min at room temperature.
Example 9
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, potassium carbonate, nitric acid and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 8.7 percent by weight/wt; the total molar concentration of potassium carbonate and nitric acid was 2mol/L (molar ratio of lithium chloride to nitric acid was 1: 1). In the case of the polyvinyl alcohol of this example, the polyvinyl alcohol was completely dissolved within 30min at 40 ℃.
Example 10
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, ammonium ferrous sulfate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 4.3 percent by weight/wt; the molar concentration of the ammonium ferrous sulfate is 2 mol/L. In the case of the polyvinyl alcohol of this example, the polyvinyl alcohol was completely dissolved within 30min at room temperature.
Example 11
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, ferric iodide and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-1797 type, and the alcoholysis degree is as follows: 97% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 11.0 percent by weight/wt; the molar concentration of iron iodide was 6 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 30min at 0 ℃.
Example 12
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, formic acid and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-2899 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 6.8 percent by weight/wt; the molar concentration of formic acid was 4 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 20min at 30 ℃.
Example 13
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, potassium thiocyanate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 9.8 percent by weight/wt; the molar concentration of the potassium thiocyanate is 2 mol/L. In the case of polyvinyl alcohol of this example, polyvinyl alcohol was completely dissolved within 10min at 20 ℃.
Example 14
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, sodium bisulfite and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-1799 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 5.8 percent by weight/wt; the molar concentration of sodium bisulfite is 3 mol/L. In the case of the polyvinyl alcohol of this example, the polyvinyl alcohol was completely dissolved within 60min at 50 ℃.
Example 15
The embodiment of the application provides a method for dissolving polyvinyl alcohol with high alcoholysis degree, which comprises the following steps:
mixing and dissolving polyvinyl alcohol, aluminum bromide and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-2899 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 7.8 percent by weight/wt; the molar concentration of the aluminum bromide is 6 mol/L. In the case of the polyvinyl alcohol of this example, the polyvinyl alcohol was completely dissolved within 10min at room temperature.
Comparative example 2
The comparative example of the application provides a contrast dissolution method, and the specific method comprises the following steps:
mixing and dissolving polyvinyl alcohol and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-2899 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of polyvinyl alcohol in the system was 3.0% wt/wt. The polyvinyl alcohol of this comparative example had a dissolution rate of 0.34% (wt/wt) at 0 deg.C, and it was found that the polyvinyl alcohol having a high alcoholysis degree could not be efficiently dissolved by using sodium hydroxide.
Comparative example 3
The comparative example of the application provides a contrast dissolution method, and the specific method comprises the following steps:
mixing and dissolving polyvinyl alcohol, sodium hydroxide and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 5.2 percent by weight/wt; the molar concentration of the sodium hydroxide is 2 mol/L; under the condition of room temperature, the dissolution amount of the polyvinyl alcohol is 0.35 percent (wt/wt), and therefore, the polyvinyl alcohol with high alcoholysis degree cannot be efficiently dissolved by adopting sodium hydroxide.
Comparative example 4
The comparative example of the application provides a contrast dissolution method, and the specific method comprises the following steps:
mixing and dissolving polyvinyl alcohol, chromium sulfate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-0599 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 2.1 percent by weight/wt; the molar concentration of the chromium sulfate is 2 mol/L; at 40 ℃, the dissolution amount of the polyvinyl alcohol is 0.09% (wt/wt), and therefore, the high alcoholysis degree polyvinyl alcohol cannot be efficiently dissolved by adopting the chromium sulfate.
Comparative example 5
The comparative example of the application provides a contrast dissolution method, and the specific method comprises the following steps:
mixing and dissolving polyvinyl alcohol, sodium citrate and pure water to obtain dissolved polyvinyl alcohol;
wherein, the polyvinyl alcohol is PVA-1799 type, and the alcoholysis degree is as follows: 99% (mol/mol);
the addition amount of the polyvinyl alcohol in the system is 3.0 percent by weight/wt; the molar concentration of the sodium citrate is 2 mol/L; at 30 ℃, the dissolution amount of the polyvinyl alcohol is 0.40% (wt/wt), and therefore, the high alcoholysis degree polyvinyl alcohol cannot be efficiently dissolved by adopting the sodium citrate.
In summary, the embodiment of the present application is a method for dissolving polyvinyl alcohol with high alcoholysis degree at normal temperature, which is simple and has many raw materials. The micromolecule additive can be recovered by a wet spinning method, a direct dialysis method, a heating recovery method, a swelling method after film formation by flow extension or a water exchange method after crosslinking, the recovered micromolecule additive can be recycled, the energy is saved, the environment is protected, and zero pollution to the environment can be realized in the dissolving process. Moreover, the dissolved polyvinyl alcohol obtained in the above embodiment can be normally used, and the properties are not different from those of the polyvinyl alcohol dissolved at high temperature, so that the normal use in various fields can be ensured.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims (5)

1. A method of dissolving high alcoholysis degree polyvinyl alcohol comprising:
mixing and dissolving polyvinyl alcohol, small molecular additives and water to obtain dissolved polyvinyl alcohol;
wherein the alcoholysis degree of the polyvinyl alcohol is more than or equal to 95% mol/mol; the final concentration of the micromolecular additive is 0.3-15 mol/L; the addition amount of the polyvinyl alcohol in the dissolving system is 2-25% wt/wt;
the small molecular additive is selected from one or more of magnesium nitrate, ferric nitrate, potassium iodide, manganese chloride, ammonium ferrous sulfate, ferric iodide, formic acid, potassium thiocyanate and aluminum bromide.
2. The method of claim 1,
the final concentration of the small molecule additive is 1-12 mol/L.
3. The method of claim 1, wherein the temperature of the mixed solution is 0-50 ℃.
4. The method of claim 1, wherein the mixing and dissolving time is 1-60 min.
5. The method of any one of claims 1 to 4, further comprising recovering the small molecule additive;
and recovering the small molecular additive from the dissolved polyvinyl alcohol by a wet spinning method, a direct dialysis method, heating recovery, a post-extension film-forming swelling method or a cross-linking post-water exchange method.
CN202110577614.6A 2021-05-26 2021-05-26 Method for dissolving polyvinyl alcohol with high alcoholysis degree Active CN113265068B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110577614.6A CN113265068B (en) 2021-05-26 2021-05-26 Method for dissolving polyvinyl alcohol with high alcoholysis degree

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110577614.6A CN113265068B (en) 2021-05-26 2021-05-26 Method for dissolving polyvinyl alcohol with high alcoholysis degree

Publications (2)

Publication Number Publication Date
CN113265068A CN113265068A (en) 2021-08-17
CN113265068B true CN113265068B (en) 2022-07-08

Family

ID=77232896

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110577614.6A Active CN113265068B (en) 2021-05-26 2021-05-26 Method for dissolving polyvinyl alcohol with high alcoholysis degree

Country Status (1)

Country Link
CN (1) CN113265068B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE728743A (en) * 1968-02-23 1969-08-21
BE728740A (en) * 1968-02-23 1969-08-21
CN105670189A (en) * 2016-02-25 2016-06-15 河南工程学院 Vinol wire used for fused deposition molding and capable of being quickly dissolved and preparation method thereof
CN107216464A (en) * 2017-06-14 2017-09-29 荆州市九天化工科技有限公司 A kind of preparation method of rapidly-soluble polyvinyl alcohol
CN110144094A (en) * 2019-06-17 2019-08-20 株洲蓝海包装有限公司 A kind of regulatable polyvinyl alcohol film of dissolving speed and preparation method thereof
CN112646206A (en) * 2020-12-21 2021-04-13 青岛大学 High-transparency polyvinyl alcohol hydrogel and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE728743A (en) * 1968-02-23 1969-08-21
BE728740A (en) * 1968-02-23 1969-08-21
CN105670189A (en) * 2016-02-25 2016-06-15 河南工程学院 Vinol wire used for fused deposition molding and capable of being quickly dissolved and preparation method thereof
CN107216464A (en) * 2017-06-14 2017-09-29 荆州市九天化工科技有限公司 A kind of preparation method of rapidly-soluble polyvinyl alcohol
CN110144094A (en) * 2019-06-17 2019-08-20 株洲蓝海包装有限公司 A kind of regulatable polyvinyl alcohol film of dissolving speed and preparation method thereof
CN112646206A (en) * 2020-12-21 2021-04-13 青岛大学 High-transparency polyvinyl alcohol hydrogel and preparation method and application thereof

Also Published As

Publication number Publication date
CN113265068A (en) 2021-08-17

Similar Documents

Publication Publication Date Title
CN110217931B (en) Recycling treatment process for waste acid
CN103882431B (en) The zero-emission recovery and treatment method of a kind of aluminium foil industry corrosion waste acid and system thereof
CN103043759B (en) Method for preparing polyaluminium ferric chloride flocculating agent by pickling waste liquid and waste aluminium material
CN101041500B (en) Highly effective reusing method for leather producing chrome tanning exhausted liquid
CN105060599A (en) Stainless steel pickling waste water resource recycling method
CN113265068B (en) Method for dissolving polyvinyl alcohol with high alcoholysis degree
CN104401978B (en) A kind of preparation method of expandable sulfur-free graphite
CN111607106A (en) Dissolving of cellulose and preparation method of regenerated cellulose
CN104524951A (en) Acid waste gas treatment and resource utilization
CN104073232B (en) Microgel stabilizer with slow release performance and preparation method of microgel stabilizer
CN114409813B (en) Green recyclable cellulose solvent, preparation method thereof and method for realizing cellulose regeneration
CN101935847B (en) Method for removing trace iodine from salt water for producing sodium hydroxide by electrolysis method
CN111517965B (en) Preparation method of p-methoxyphenylethylamine
CN108793356B (en) Preparation method of polymeric ferric sulfate crystal for treating industrial wastewater
CN115611996B (en) Preparation method of regenerated chitin
CN105148710A (en) Absorption method of tail gas produced in production of trichloroacetyl chloride by means of chlorination process
CN113247921A (en) Combined denitration process for chlor-alkali and sodium chlorate
CN114409036A (en) Method for reducing content of chloride ions in circulating water in chlor-alkali chemical industry
TWI696309B (en) Method for preparing and purifying lithium carbonate from waste lithium battery
CN221217418U (en) Byproduct salt recovery device in production of hydrazine hydrate by urea method
CN104371032A (en) Crosslinked starch xanthate, and preparation method and application thereof
CN111704745B (en) Method for recycling sea material in sea-island fiber
CN113368676B (en) Flue gas desulfurization and denitrification integrated treatment method
CN110639575A (en) Cu2+Preparation method of doped amorphous alkali type nickel carbonate
CN116102746B (en) Method for dissolving cellulose based on proton type ionic liquid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant