CN107216464B - A kind of preparation method of rapidly-soluble polyvinyl alcohol - Google Patents
A kind of preparation method of rapidly-soluble polyvinyl alcohol Download PDFInfo
- Publication number
- CN107216464B CN107216464B CN201710447556.9A CN201710447556A CN107216464B CN 107216464 B CN107216464 B CN 107216464B CN 201710447556 A CN201710447556 A CN 201710447556A CN 107216464 B CN107216464 B CN 107216464B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- rapidly
- soluble polyvinyl
- preparation
- parts
- 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
Links
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The present invention discloses a kind of preparation method of rapidly-soluble polyvinyl alcohol, by polyvinyl alcohol raw material, add in water acetic acid methyl esters, and appropriate alcoholysis agent, stabilizer and organic slat solution, it adds in stirred tank and is sufficiently mixed, by mediating machine equipment high temperature extrusion, moisture is made to be fully infiltrated into material, it is swollen material, volume increases 1 to 3 times, and floccule is ground into after then being dried by the tape casting.Polyvinyl alcohol can be completely dissolved under the conditions of 95 98 DEG C within half an hour caused by present invention processing, and a large amount of processing costs for saving next process shorten the production time, improve production efficiency, achieve the effect that energy-saving and emission-reduction.
Description
Technical field
The present invention relates to polyvinyl alcohol fields, and in particular to a kind of preparation method of rapidly-soluble polyvinyl alcohol.
Background technology
Polyvinyl alcohol, alias PVA, being uniquely can be by bacterium as carbon source and the polyvinyl of using energy source, thin
Under the action of bacterium and enzyme, 46 days degradable 75%, belong to a kind of Biodegradable polymer material, be often used as polyvinyl alcohol
Film or aqueous binder can be mass produced by Non oil-based route, cheap, oil resistant, solvent resistant and gas barrier property
It is outstanding, there is unique advantage in terms of food, Key works Drug packing.The application of PVA is based on solwution method, and film is prepared by casting film-forming
Material, but solution machine-shaping need to undergo dissolving and drying process, there are the shortcomings of complex process, of high cost, low output, very
Difficulty prepares heavy wall, complex-shaped product, meanwhile, it also can not carry out coextrusion blow with other materials and prepare multi-layer compound film.
Since polyvinyl alcohol cannot be stabilized with free state, polyvinyl alcohol (PVA) can not possibly directly gather from vinyl alcohol
Conjunction obtains, and carries out alcoholysis under base catalysis to prepare mostly using polyvinyl acetate at present, that is, the poly- second of low polymerization degree to be prepared
Enol (PVA) must first prepare the polyvinyl acetate of low polymerization degree.
In the prior art in order to improve the performance of polyvinyl alcohol product, the second polymerized monomer is added in polymerisation in solution
Graft copolymerization is carried out, polyvinyl acetate strand is made to introduce second comonomer, then carries out alcoholysis and prepares modified polyethylene
Alcohol.
Patent 200810153707 discloses a kind of preparation method of polyvinyl alcohol with low degree of polymerization, using acetaldehyde as molecule
Conditioning agent manufacture polyvinyl alcohol with low degree of polymerization is measured, Suspension alcoholysis is carried out as suspending agent using alkane, manufactures powdery polyethylene
Alcohol, alcoholysis degree scope 72.4-77.9%.The recycling of this method suspending agent is difficult.
Patent CN01115186.2 discloses a kind of preparation method of polyvinyl alcohol with low alcoholysis level, by esters, ethers, ketone
Class, hydro carbons etc. are in the polyvinyl acetate alcoholysis reaction system that solvent is added to using methanol as solvent, after completion of the reaction again
The alcoholysis degree that product is precipitated in polyvinyl alcohol with low alcoholysis level by condensation agent is added to be 50~90%.
It is equivalent to above-mentioned two method and the third substance (or even the 4th kind) is all with the addition of in polymerization and alcoholysis process, this
The method of invention is simple for process, and convenient for control, solvent is easily recycled product quality, it is at low cost the advantages that.
Also the useful high-alkali alcoholysis method of twin-screw alcoholysis machine can produce cotton-shaped polyvinyl alcohol to the prior art, in production process into
Mechanical crushing is gone.The characteristics of high-alkali alcoholysis method be the water dissolution of alcoholysis catalysts sodium hydroxide (concentration for 300-350 grams/
Rise), the usage amount of catalyst is higher (molar ratio 0.12% or so), and alcoholysis speed is fast (20-60 seconds), produces high alcoholysis degree
The polyvinyl alcohol of (more than 99.8%).Specific practice is：By the methanol solution (concentration 25% or so) of polyvinyl acetate with urging
Agent (300-350 g/l of sodium hydrate aqueous solution) is stirred, and alcoholysis reaction (reactant occurs in screw rod alcoholysis machine
Residence time in alcoholysis machine is very short), then by product after crushing three times, squeezing is gathered after being dried into drying machine
Vinyl alcohol.
The polyvinyl alcohol that various processing methods in the above process obtain, solubility property is poor, adds in further production
, it is necessary to which reaction kettle high temperature rises to 95-98 DEG C during work, two hours then are kept the temperature, is fully used after dissolving.During this,
It needs to consume the substantial amounts of energy, virtually adds production cost, cause the loss of human and material resources, while generate a large amount of
Exhaust gas cause air pollution.If further improving solution temperature, polyvinyl alcohol may be caused brittle, lose effect.
Now it is badly in need of a kind of rapidly-soluble polyvinyl alcohol material of energy of research and development.
The content of the invention
For the deficiency in the presence of the prior art, the present invention provides a kind of preparations of the rapidly-soluble polyvinyl alcohol of energy
Method makes material fully be swollen, improves the solubility property of material by a series of physical method.
To achieve the above object, present invention employs following technical solutions：
A kind of preparation method of rapidly-soluble polyvinyl alcohol has following steps：
(1) 100 parts of polyvinyl alcohol raw materials, the water and 2-5 parts of methyl acetate of 5-20 parts of addition and 2-5 parts of alcohol are chosen
Agent, 1-2 parts of stabilizers and 1-2 parts of organic slat solutions are solved, adds in stirred tank, is stirred to form colloid at normal temperatures, and it is quiet
Put 2-3 hour；
(2) gained colloid in step (1) is placed in kneader, is kept the temperature under 40-60 DEG C, 1.2 atmospheric pressure 1-2 small
When, 95-98 DEG C, when heat preservation 2-4 is small is then raised temperature to, the semi-finished product being fully swollen；
(3) gained semi-finished product in step (2) are dried and crushes to obtain the rapidly-soluble polyvinyl alcohol of energy.
Preferably, the alcoholysis agent in the step (1) is the ethanol solution or methanol solution of alkalescence, stabilizer is acetic acid
Ethylene, organic slat solution are the sodium acetate solution that mass-volume concentration is 1%-3%.
Preferably, the stirred tank rotating speed in the step (1) is 40-70r/min.
Preferably, the stirred tank is divided into two layers, outer layer is recirculated water, and internal layer is provided with reflux, in stirred tank
The heart sets several agitating paddles being twist centrally located on axis, is provided with and the agitating paddle hand of spiral on the inner wall of stirred tank
Opposite helical structure, agitating paddle are in strip, and several cross-shaped through hole are set on agitating paddle, and cross-shaped through hole intersection is set
Hollow ball, hollow ball are connected with through-hole side wall by spring.
Preferably, the kneader is double seal formula structure, outside is recirculated water, and circulation waterway is provided with temperature
Table；Internal layer is provided with safety valve and air gauge filled with nitrogen, internal layer nitrogen charging mouth, and internal layer is additionally provided with cooling and reflux device.
Preferably, the dwell temperature in the step (1) is 20 DEG C.
Preferably, the heating in the step (1) uses immersion method.
Preferably, furnace drying method is the tape casting in the step (3).
Preferably, the rapidly-soluble polyvinyl alcohol of energy obtained in the step (3) is in cotton-shaped.
Polyvinyl alcohol is a kind of network polymers, the high polymer diffusion of macromolecular chain to solvent direction in dissolving, because dividing
Subchain length is very restricted, and solvent molecule is then readily permeable into high polymer, therefore the course of dissolution one of high polymer
As to pass through infiltration --- swelling and dissolving --- and disperse two stages.The dissolving of PVA should also carry out in two stages, molten at present
The method for solving PVA, only emphasizes that boiling for dissolution phase stirs the time, without fully infiltrating --- the time of swelling.
Polyvinyl alcohol, if the i.e. spontaneous progress of PVA course of dissolution energy, could quickly and evenly dissolve.High polymer can it is spontaneous into
Row dissolving conditional be：
ΔFM<0 and Δ FM=Δ HM-T Δs SM
In formula:
Δ FM --- free energy of mixing variable；
T --- solution temperature；
Δ HM --- enthalpy of mixing variable；
Δ SM --- entropy of mixing variable.
Without apparent neither endothermic nor exothermic phenomenon when PVA dissolves, temperature during dissolving is also constant, enthalpy change Δ H and T in institute's above formula
It can ignore, so influence the only Δ SM values of Δ FM values.I.e. Entropy Changes Δ S absolute values are more big more favourable spontaneous dissolving.
According to thermodynamic consideration, the variation of intermolecular force, the variation of molecular motion degrees of freedom is all straight with Entropy Changes Δ S
It is connected to pass.For PVA after fully swelling, a large number of water molecules penetrates into PVA inside configurations, and partial moisture is carried out with hydroxyl OH
Association, and PVA structures is promoted to expand, the result is that distance between macromolecule increases, intermolecular reaction force attenuation, molecule from
Increased by movement, the variation of these factors all increases Entropy Changes Δ S absolute values.Because the increase of Entropy Changes value can promote the spontaneous of PVA dissolvings
It carries out, therefore fully swelling can be such that PVA quickly dissolves.
The present invention utilize polyvinyl alcohol swellability, make under certain conditions polymeric chain molecular structure be filled into it is organic
Molecules of salt and hydrone, make volume of material become larger, and each intermolecular force of polymeric chain is made to become smaller, is conducive to dissolve.Due to organic
The effect of salt, inside and outside the polymer between generate osmotic pressure.Since external solution concentration is dense less than internal solution during dissolving
Degree so water can enter from external inside molecular structure, makes polymer have water imbibition, and the concentration difference of the two is bigger,
The osmotic pressure of generation is also bigger, and solubility property is also better, and the means using industrial technology are that polyvinyl alcohol is fully swollen.
Polyvinyl alcohol can be completely dissolved, great Liang Jie under the conditions of 95-98 DEG C within half an hour caused by present invention processing
The about processing cost of next process shortens the production time, improves production efficiency, achievees the effect that energy-saving and emission-reduction.
Description of the drawings
Fig. 1 is a kind of structure type schematic diagram of agitating paddle in the embodiment of the present invention.
Fig. 2 is the microstructure partial enlarged view of agitating paddle in Fig. 1.
Reference numeral is as follows：
1st, central shaft, 2, agitating paddle, 3, hollow ball, 4, spring
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Polyvinyl alcohol can be dissolved in water at 95 DEG C or more, but when the temperature is excessively high, and can make molecular link that fracture failure occur,
Therefore it can only use and dissolving is kept the temperature in the environment of 95-98 DEG C.The present invention utilizes the swellability of polyvinyl alcohol, in certain condition
Under the molecular structure of polymeric chain is made to be filled into organic molecules of salt and hydrone, volume of material is made to become larger, makes polymeric chain each intermolecular
Active force becomes smaller, and is conducive to dissolve.Due to the effect of organic salt, inside and outside the polymer between generate osmotic pressure.During dissolving
Since external solution concentration is less than internal solution concentration, so water can enter from external inside molecular structure, there is polymer
Water imbibition, and the concentration difference of the two is bigger, and the osmotic pressure of generation is also bigger, and solubility property is also better.Due to existing poly-
Vinyl alcohol is made of vinyl acetate (VAc) aggregated alcoholysis, and usually there are two types of raw material route, one kind is using ethylene as original
Material, preparing vinyl acetate, then polyvinyl alcohol is made；Another is for raw material with acetylene (being divided into carbide acetylene and gas acetylene)
Prepare vinyl acetate, then polyvinyl alcohol be made, thus in order to prevent prolonged high temperature and pressure make material occur property become, it is necessary to plus
Enter suitable alcoholization agent and stabilizer, alcoholization agent is usually methanol or ethyl alcohol, and property caused by hydroxyl is broken in order to prevent becomes；
Stabilizer generally use vinyl acetate increases the emulsification degree of mixed solution, convenient for the abundant swelling of finished product.
Embodiment 1：
(1) 100 parts of polyvinyl alcohol raw materials are chosen, add in 5 parts water and 5 parts of methyl acetate and 5 parts of alcoholysis agents, 1 part
Stabilizer and 1 part of organic slat solution add in stirred tank, are stirred to form colloid at normal temperatures, and stand 2-3 hour；
(2) gained colloid in step (1) is placed in kneader, 1-2 hour is kept the temperature under 40-60 DEG C, 0.4Mpa, with
After be warming up to 95-98 DEG C, when heat preservation 2-4 is small, the semi-finished product that are fully swollen；
(3) gained semi-finished product in step (2) are dried and crushes to obtain the rapidly-soluble polyvinyl alcohol of energy.
Embodiment 2：
(1) 100 parts of polyvinyl alcohol raw materials, the water and 2 parts of methyl acetate of 20 parts of addition and 2 parts of alcoholysis agents, 2 are chosen
Part stabilizer and 2 parts of organic slat solutions add in stirred tank, are stirred to form colloid at normal temperatures, and stand 2-3 small
When；
(2) gained colloid in step (1) is placed in kneader, is kept the temperature under 40-60 DEG C, 1.2 atmospheric pressure 1-2 small
When, 95-98 DEG C, when heat preservation 2-4 is small is then raised temperature to, the semi-finished product being fully swollen；
(3) gained semi-finished product in step (2) are dried and crushes to obtain the rapidly-soluble polyvinyl alcohol of energy.
Embodiment 3：
(1) 100 parts of polyvinyl alcohol raw materials of selection, the water and 4 parts of methyl acetate of 10 parts of addition and 1.5 parts of alcoholysis agents,
1.5 parts of stabilizers and 1.5 parts of organic slat solutions add in stirred tank, are stirred to form colloid at normal temperatures, and stand 2-3
A hour；
(2) gained colloid in step (1) is placed in kneader, is kept the temperature under 40-60 DEG C, 1.2 atmospheric pressure 1-2 small
When, 95-98 DEG C, when heat preservation 2-4 is small is then raised temperature to, the semi-finished product being fully swollen；
(3) gained semi-finished product in step (2) are dried and crushes to obtain the rapidly-soluble polyvinyl alcohol of energy.
In above-described embodiment, due to the unstability of polyvinyl alcohol, during stirring, stirred tank is divided into two layers, and outer layer is cycle
The heating water bath of formula, for being kept stirring the temperature of kettle, internal layer is provided with reflux, during concrete operations, first by polyvinyl alcohol
Raw material and water, which are added in stirred tank, stirs into colloidal, and alcoholysis agent, stabilizer or other additives are then gradually added portionwise again,
Prevent from stirring it is insufficient, whole mixing time not less than 6 it is small when, be sufficiently mixed material.
Stirred tank centrally disposed several agitating paddles 2 being twist centrally located on axis 1 are then set on the inner wall of stirred tank
It is equipped with the screw mechanism opposite with 2 hand of spiral of agitating paddle, during stirring, the material near central shaft 1 can be made along agitating paddle 2
The hand of spiral stir, outside is then overturn in reverse direction, is formed the cycling up and down of material, is made stirring more abundant；Agitating paddle 2 is in
Strip since resistance is larger when rotating is stirred, sets several cross-shaped through hole on agitating paddle, cross-shaped through hole intersection is set
Hollow ball 3, hollow ball are connected with through-hole side wall by spring 4, with agitating paddle rotation direction on the contrary, for current limliting during work, and
Improve mixing effect.
Kneader main part is the structure of double seal formula, and outside is circulating water-cooling heating or heat preservation, prevents part
Overheat causes material generation property to become, and filled with nitrogen, internal layer reaction mechanism is additionally provided with cooling and reflux device, prevents material for inside
Air pressure and temperature when volatilizing loss, external air gauge and thermometer can control kneading.
In a preferred embodiment of the invention, ethanol solution or the first that the alcoholysis agent in the step (1) is 90%
Alcoholic solution, stabilizer are vinyl acetate, and organic slat solution is the sodium acetate solution that mass-volume concentration is 1%-3%.
In a preferred embodiment of the invention, the stirred tank rotating speed in the step (1) is 40-70r/min, specifically
Speed determines that volume is bigger according to the liquor capacity in stirred tank, and speed is slower, and mixing time is longer.
In a preferred embodiment of the invention, the dwell temperature in the step (1) is 20 DEG C.
In a preferred embodiment of the invention, furnace drying method is the tape casting in the step (3).
In a preferred embodiment of the invention, the heating in the step (1) uses immersion method.
In a preferred embodiment of the invention, the rapidly-soluble polyvinyl alcohol of energy obtained in the step (3) is in
It is cotton-shaped.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail in good embodiment, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and scope of technical solution of the present invention, should all be covered at this
Among the right of invention.
Claims (9)
1. a kind of preparation method of rapidly-soluble polyvinyl alcohol, which is characterized in that there are following steps：
(1) 100 parts of polyvinyl alcohol raw materials of selection, the water and 2-5 parts of methyl acetate of 5-20 parts of addition and 2-5 parts of alcoholysis agents,
1-2 parts of stabilizers and 1-2 parts of organic slat solutions are added in stirred tank, when stirring 6-8 is small at normal temperatures, is formed colloid, and are stood
2-3 hour；
(2) gained colloid in step (1) is placed in kneader, 1-2 hour is kept the temperature under 40-60 DEG C, 1.2 atmospheric pressure,
95-98 DEG C, when heat preservation 2-4 is small is then raised temperature to, the semi-finished product being fully swollen；
(3) gained semi-finished product in step (2) are dried and crushes to obtain the rapidly-soluble polyvinyl alcohol of energy.
A kind of 2. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(1) alcoholysis agent in is the ethanol solution or methanol solution of alkalescence, and stabilizer is vinyl acetate, and organic slat solution is quality volume
Concentration is the sodium acetate solution of 1%-3%.
A kind of 3. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(1) the stirred tank rotating speed in is 40-70r/min.
4. the preparation method of a kind of rapidly-soluble polyvinyl alcohol as described in claim 1 or 3, which is characterized in that described to stir
It mixes kettle to be divided into two layers, outer layer is recirculated water, and internal layer is provided with reflux, and stirred tank is centrally disposed several to be twist distributed in
Agitating paddle on central shaft is provided with the helical structure opposite with the agitating paddle hand of spiral, agitating paddle on the inner wall of stirred tank
In strip, several cross-shaped through hole are set, cross-shaped through hole intersection sets hollow ball, hollow ball and through-hole side wall on agitating paddle
It is connected by spring.
A kind of 5. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the kneader
For double seal formula structure, outside is recirculated water, and circulation waterway is provided with thermometer；Internal layer is set filled with nitrogen, internal layer nitrogen charging mouth
Safety valve and air gauge are equipped with, internal layer is additionally provided with cooling and reflux device.
A kind of 6. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(1) dwell temperature in is 20 DEG C.
A kind of 7. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(2) heating in uses immersion method.
A kind of 8. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(3) furnace drying method is the tape casting in.
A kind of 9. preparation method of rapidly-soluble polyvinyl alcohol as described in claim 1, which is characterized in that the step
(3) the rapidly-soluble polyvinyl alcohol of energy obtained in is in cotton-shaped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447556.9A CN107216464B (en) | 2017-06-14 | 2017-06-14 | A kind of preparation method of rapidly-soluble polyvinyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447556.9A CN107216464B (en) | 2017-06-14 | 2017-06-14 | A kind of preparation method of rapidly-soluble polyvinyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107216464A CN107216464A (en) | 2017-09-29 |
| CN107216464B true CN107216464B (en) | 2018-06-01 |
Family
ID=59948463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710447556.9A Active CN107216464B (en) | 2017-06-14 | 2017-06-14 | A kind of preparation method of rapidly-soluble polyvinyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107216464B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100316B (en) * | 2018-10-25 | 2022-11-11 | 中国石油化工股份有限公司 | Hollow polyvinyl alcohol particles and preparation method thereof |
| CN111100306B (en) * | 2018-10-25 | 2022-11-08 | 中国石油化工股份有限公司 | Preparation method of hollow polyvinyl alcohol particles |
| CN112094366A (en) * | 2020-09-27 | 2020-12-18 | 安徽皖维高新材料股份有限公司 | Preparation method of easily-soluble flocculent polyvinyl alcohol |
| CN113265068B (en) * | 2021-05-26 | 2022-07-08 | 中山大学 | Method for dissolving polyvinyl alcohol with high alcoholysis degree |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164251A (en) * | 1994-08-05 | 1997-11-05 | 艾索利塞有限公司 | Method of manufacturing monolithic structures from polyvinyl alcohol |
| KR20100138503A (en) * | 2009-06-25 | 2010-12-31 | 이화여자대학교 산학협력단 | Improved preparation method of pva nanofiber membrane using electrospinning |
| CN102827316A (en) * | 2012-09-05 | 2012-12-19 | 安徽皖维集团有限责任公司 | Preparation method for polyvinyl alcohol with low crystallinity |
| CN103483598A (en) * | 2013-09-26 | 2014-01-01 | 重庆理工大学 | Method for accelerating polyvinyl alcohol dissolution |
| CN103772862A (en) * | 2014-01-08 | 2014-05-07 | 华南理工大学 | Partial alcoholysis type polyvinyl alcohol powder easy to disperse in water and preparation method thereof |
-
2017
- 2017-06-14 CN CN201710447556.9A patent/CN107216464B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164251A (en) * | 1994-08-05 | 1997-11-05 | 艾索利塞有限公司 | Method of manufacturing monolithic structures from polyvinyl alcohol |
| KR20100138503A (en) * | 2009-06-25 | 2010-12-31 | 이화여자대학교 산학협력단 | Improved preparation method of pva nanofiber membrane using electrospinning |
| CN102827316A (en) * | 2012-09-05 | 2012-12-19 | 安徽皖维集团有限责任公司 | Preparation method for polyvinyl alcohol with low crystallinity |
| CN103483598A (en) * | 2013-09-26 | 2014-01-01 | 重庆理工大学 | Method for accelerating polyvinyl alcohol dissolution |
| CN103772862A (en) * | 2014-01-08 | 2014-05-07 | 华南理工大学 | Partial alcoholysis type polyvinyl alcohol powder easy to disperse in water and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107216464A (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216464B (en) | A kind of preparation method of rapidly-soluble polyvinyl alcohol | |
| CN103937234B (en) | Heat-conducting plastic of a kind of applying modified carbon material and preparation method thereof | |
| CN101200393B (en) | Membrane material for producing coated material and preparation technique thereof | |
| CN106106522A (en) | A kind of nano zine oxide carries silver chitosan compound anti-bacteria agent and preparation method thereof | |
| CN110467724B (en) | Preparation method of semi-aromatic nylon | |
| CN103709267A (en) | Preparation method of dialdehyde carboxymethyl chitosan | |
| CN107353605A (en) | A kind of multifunctional graphite vinyl/PET composite membranes and preparation method thereof | |
| CN101108894B (en) | Polymerization processor | |
| CN109021948A (en) | A kind of preparation method of novel heavy crude thinner | |
| CN104774454A (en) | High-temperature-resistant nylon PA66T material and preparation method thereof | |
| CN110982062A (en) | Preparation method of low molecular weight polyether ether ketone | |
| Fukuoka et al. | Bioprocessing of glycerol into glyceric acid for use in bioplastic monomer | |
| CN108424538B (en) | Preparation method of cellulose/nano-attapulgite composite barrier film | |
| CN108752633A (en) | Polylactic acid modified stannic oxide/graphene nano composite material and preparation method and application | |
| CN110004195B (en) | Method for preparing octenyl succinic acid starch ester by enzymatic auxiliary extrusion | |
| CN108219036B (en) | A kind of polyvinyl alcohol ester and the preparation method and application thereof | |
| CN111592616A (en) | Preparation method of nanoscale hyperbranched hydrophobically associating polyacrylamide | |
| CN206661212U (en) | It is a kind of can fast cooling polymerization reaction kettle | |
| CN113025296B (en) | Method for preparing W/O/W type nano oil displacement agent by adopting micro-flow field reaction technology | |
| CN102344511B (en) | Modified synthesis method for high-viscosity film forming resin with dielectric property | |
| CN103601886B (en) | A kind of preparation method of poly-[2,5-dihydroxy-1,4-pyridobismidazole] polymkeric substance | |
| CN109553769B (en) | Para-aramid resin continuous polymerization system and method thereof | |
| CN103570941B (en) | A kind of Nano polyamide composite and production method thereof | |
| CN103951816B (en) | In-situ polymerization strengthens the preparation method of carbon nanotube/semiaromatic type TLCP matrix material | |
| CN106589191A (en) | High molecular weight polyacrylonitrile homopolymer preparation method |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190930 Address after: Qianfeng industrial concentration zone, Xinhuang Dong Autonomous County, Huaihua City, Hunan Province Patentee after: Hunan Anxiang Technology Co., Ltd. Address before: 434000 No. five, weft Road, Jingzhou Development Zone, Hubei, Jingzhou Patentee before: Jingzhou nine days Chemical Technology Co., Ltd. |
|
| TR01 | Transfer of patent right |