CN107163463A - A kind of polyvinyl alcohol compositions of melt-processable and preparation method thereof - Google Patents
A kind of polyvinyl alcohol compositions of melt-processable and preparation method thereof Download PDFInfo
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- CN107163463A CN107163463A CN201710419247.0A CN201710419247A CN107163463A CN 107163463 A CN107163463 A CN 107163463A CN 201710419247 A CN201710419247 A CN 201710419247A CN 107163463 A CN107163463 A CN 107163463A
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- polyvinyl alcohol
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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)
Abstract
A kind of polyvinyl alcohol compositions of melt-processable, said composition component is：Polyvinyl alcohol, phosphate compounds, the weight ratio between them are 70~99：30~1.The degree of polymerization of the polyvinyl alcohol is 500~2400, and alcoholysis degree is 85~100%.The preparation method of the polyvinyl alcohol compositions is：Polyvinyl alcohol is pre-mixed with phosphate compounds, then mixed material addition extruder is extruded, by the material pelletizing of extrusion, thermoplastic polyvinyl alcohol composition is made.Another preparation method is：Polyvinyl alcohol is put into distilled water and is configured to homogeneous solution, portion rate on request is weighed in addition phosphate compounds poly-vinyl alcohol solution, it is agitated well mixed, dry；Then dried compound is put into extruder, direct extruding pelletization, thermoplastic polyvinyl alcohol composition is made.The polyvinyl alcohol compositions of preparation can be used for preparing fibre, film product, hollow container, tubing.
Description
Technical field
The invention belongs to chemical products field, the polyvinyl alcohol compositions of more particularly to a kind of melt-processable and its preparation
Method.
Background technology
Polyvinyl alcohol (PVA) is a kind of high molecular weight water soluble polymer that can be mass produced by Non oil-based route.Poly- second
Great amount of hydroxy group in enol molecule makes it have excellent oil resistant, solvent resistant and gas barrier property, food, medicine, agricultural chemicals,
There is unique advantage in terms of the packed and transporteds such as hydro carbons reagent.However, due to easily forming substantial amounts of between PVA macromolecular chain adjacent hydroxyl groups
Intramolecular and intermolecular hydrogen bonding, make its heat decomposition temperature (200-250 DEG C) be approached for (220-240 DEG C) with fusing point, are sent out during melting
Heat is decomposed, therefore, it is difficult to melt-processed, and typically uses solution spinning, casting film-forming method, and this kind of processing method is only capable of
Low-dimensional product (such as film, fiber etc.) is prepared, and processing technology complexity, high energy consumption, cost are high, significantly limit PVA
Application and development.
In terms of current research conditions, it is to realize PVA melt-processeds most to add small-molecule substance or oligomer plasticizer
For effective and direct method.The small-molecule substance or oligomer of addition can weaken with the formation hydrogen bond of the hydroxyl on PVA strands
PVA intramoleculars and intermolecular active force, to reduce fusing point, improve PVA fluidity of molten, realize melt-processed.Such as Japan
Patent JP77110782 reports the melt-blown polyvinyl alcohol film build method that a kind of water makees plasticizer, but water makees plasticizer
Heat endurance is poor, and process easily produces bubble, causes film not to be molded uniformly.Chinese patent CN1368515A is disclosed
A kind of new speed increasing method for thermoplastic processing polyvinyl alcohol film, this method mainly selects a kind of polymerizable amide-type
Monomer is as plasticizer, and the more presence in the form of combining water in resin of control water, so as to significantly reduce PVA trees
The processing temperature of fat, but the plasticizer that this method is selected easily is migrated, and with certain toxicity, make the film of preparation uncomfortable
Food package film is done in conjunction.Chinese patent application CN103724899A discloses a kind of thermal plasticizing polyvinyl alcohol modified material
Material, this is material modified by 100 parts of polyvinyl alcohol, 20-60 parts of composite elasticizer, 0.5-1 parts of composite antioxidant, heat stabilizer 0.1-
1 part, reinforcing agent nanometer si020.5-3 parts of compositions.Its composite elasticizer is the compounding of glycerine, polyethylene glycol and dimethyl sulfoxide (DMSO)
Thing, the material modified preparation technology is complicated, and purposes narrow is mainly used in the production of film.
The content of the invention
The purpose of the present invention be for existing melt-processable polyvinyl alcohol material weak point there is provided one kind it is fusible
Melt polyvinyl alcohol compositions of processing and preparation method thereof.
On the one hand phosphate compound has stronger inoxidizability, can capture high polymer material and be produced under heat effect
Hydroxyl radical free radical etc. and remove rapidly, so as to improve its heat endurance.On the other hand plasticizer can also be served
Effect, can reduce PVA fusing point, so as to widen PVA thermoplastic processing window.
The present invention improves PVA heat decomposition temperature by adding phosphate compounds, and reduction PVA composites melt
Point, widens PVA melt-processed window, realizes melt-processed, and the polyvinyl alcohol compositions can by the method for melt-processed
Film, fiber, tubing, container etc. is made, for packaging fields such as food, medicine, grain, dried food and nuts.
It is a further object of the present invention to provide the polyvinyl alcohol compositions of melt-processable made from above-mentioned preparation method.
The technical scheme for realizing the object of the invention is such：
A kind of polyvinyl alcohol compositions of melt-processable, said composition compounding ingredients are：Polyvinyl alcohol, phosphoric acid ester
Compound, the weight ratio between them is 70~99：30~1.
The degree of polymerization of described polyvinyl alcohol is 500~2400, and alcoholysis degree is 85~100%.
The general structure of described phosphate compounds is as follows：
In formula, R is C1~C30 alkyl chain, alkaryl chain or fatty alcohol alkyl chain, alkaryl chain, and M is oxirane
(EO) or expoxy propane (PO), R1, R2 are H or M, n are 1~30.
The preparation method of the polyvinyl alcohol compositions is：Polyvinyl alcohol is pre-mixed with phosphate compounds,
Then mixed material addition extruder is extruded, by the material pelletizing of extrusion, thermoplastic polyvinyl alcohol combination is made
Thing.
The preparation method of the polyvinyl alcohol compositions is：Polyvinyl alcohol is put into distilled water and is configured to homogeneous solution,
Weighed again by the portion rate of claim 1 requirement in addition phosphate compounds poly-vinyl alcohol solution, it is agitated it is well mixed,
Dry；Then dried compound is put into extruder, direct extruding pelletization, thermoplastic polyvinyl alcohol combination is made
Thing；Wherein extrusion temperature is 140-240 DEG C.
The purposes of described polyvinyl alcohol compositions, for preparing fibre, film product, hollow container, tubing or piece
Material.
Compared with prior art, the present invention is beneficial has technical effect that：
(1) present invention can both capture PVA by thermogenetic hydroxyl free by adding a small amount of phosphate compounds
Base, so as to improve PVA heat endurance；The effect of plasticizer can be served again, PVA fusing point can be reduced, so as to widen
PVA thermoplastic processing window.
(2) phosphate compounds that the present invention is added, content is less and will not separate out and migrate, and can widen significantly
Its application.In addition, a small amount of phosphate compounds of addition, polyvinyl alcohol can still keep excellent mechanical property.
(3) preparation is simple by the present invention, and preparation process energy consumption is small, is easy to operation.
(4) polyvinyl alcohol compositions of the present invention are widely used, available for preparing fibre, film product, hollow container, pipe
Material or sheet material.
Embodiment
The embodiment combination example below of the present invention is described in further detail.
Embodiment 1
The polyvinyl alcohol and 900g distilled water for weighing 99g are dissolved by heating at 95 DEG C, then by 5g alkyl phenol polyoxy second
Alkene ether (4) phosphate (NP-4P) is added to be uniformly mixed in solution, is then poured into mixed solution in container, at 60 DEG C
Vacuum drying obtains sample, carries out hot-forming preparation standard batten, and tensile property test is carried out by GB-13022 standards, uses
Thermal gravimetric analyzer and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.
The tensile strength of gained sample is 53MPa, and tension fracture elongation rate is 386%, and heat decomposition temperature is 286 DEG C, is melted
Point is 195 DEG C.
Embodiment 2
Weigh 99g polyvinyl alcohol to dissolve by heating at 95 DEG C with 900g distilled water, then by 5g APESs
(10) phosphate (NP-10P) is added is uniformly mixed in solution, then pours into mixed solution in container, true at 60 DEG C
Sky is dried to obtain sample, carries out hot-forming preparation standard batten, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.
The tensile strength of gained sample is 50MPa, and tension fracture elongation rate is 362%, and heat decomposition temperature is 302 DEG C, is melted
Point is 204 DEG C.
Embodiment 3
Weigh 99g polyvinyl alcohol to dissolve by heating at 95 DEG C with 900g distilled water, then by 5g APESs
(15) phosphate (NP-15P) is added is uniformly mixed in solution, then pours into mixed solution in container, true at 60 DEG C
Sky is dried to obtain sample, carries out hot-forming preparation standard batten, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.
The tensile strength of gained sample is 48MPa, and tension fracture elongation rate is 348%, and heat decomposition temperature is 314 DEG C, is melted
Point is 215 DEG C.
Embodiment 4
Weigh 90 parts of polyvinyl alcohol, 10 parts of addition homogenizers of APES (4) phosphate (NP-4P)
In, it is sufficiently mixed uniform, obtained compound；Then compound is put into extruding pelletization in single screw extrusion machine, and thermoplastic poly is made
Vinyl alcohol compositions, then hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.Wherein extruder temperature is 200 DEG C, screw rod
Rotating speed is 100rpm, and die temperature is 190 DEG C, and pelleter hauling speed is 10rpm.
The tensile strength of gained sample is 52MPa, and tension fracture elongation rate is 364%, and heat decomposition temperature is 283 DEG C, is melted
Point is 198 DEG C.
Embodiment 5
Weigh 90 parts of polyvinyl alcohol, 10 parts of addition homogenizers of APES (10) phosphate (NP-10P)
In, it is sufficiently mixed uniform, obtained compound；Then compound is put into extruding pelletization in single screw extrusion machine, and thermoplastic poly is made
Vinyl alcohol compositions, then hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.Wherein extruder temperature is 200 DEG C, screw rod
Rotating speed is 100rpm, and die temperature is 195 DEG C, and pelleter hauling speed is 10rpm.
The tensile strength of gained sample is 49MPa, and tension fracture elongation rate is 343%, and heat decomposition temperature is 300 DEG C, is melted
Point is 206 DEG C.
Embodiment 6
Weigh 90 parts of polyvinyl alcohol, 10 parts of addition homogenizers of APES (15) phosphate (NP-15P)
In, it is sufficiently mixed uniform, obtained compound；Then compound is put into extruding pelletization in single screw extrusion machine, and thermoplastic poly is made
Vinyl alcohol compositions, then hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.Wherein extruder temperature is 220 DEG C, screw rod
Rotating speed is 100rpm, and die temperature is 210 DEG C, and pelleter hauling speed is 10rpm.
The tensile strength of gained sample is 47MPa, and tension fracture elongation rate is 321%, and heat decomposition temperature is 312 DEG C, is melted
Point is 220 DEG C.
Embodiment 7
Weigh 99g polyvinyl alcohol to dissolve by heating at 95 DEG C with 900g distilled water, then by 5g APESs
(10) phosphate (NP-10P) is added is uniformly mixed in solution, then pours into mixed solution in container, true at 60 DEG C
Sky is dried to obtain sample, carries out hot-forming preparation standard batten, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.
The tensile strength of gained film is 48MPa, and tension fracture elongation rate is 419%, and heat decomposition temperature is 327 DEG C, is melted
Point is 196 DEG C.
Embodiment 8
Weigh 90 parts of polyvinyl alcohol, 10 parts of addition homogenizers of APES (10) phosphate (NP-10P)
In, it is sufficiently mixed uniform, obtained compound；Then compound is put into extruding pelletization in single screw extrusion machine, and thermoplastic poly is made
Vinyl alcohol compositions, then hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using heat
Zero-g aircraft instrument and mistake scanning calorimeter test its heat decomposition temperature and fusing point respectively.Wherein extruder temperature is 200 DEG C, screw rod
Rotating speed is 100rpm, and die temperature is 190 DEG C, and pelleter hauling speed is 10rpm.
The tensile strength of gained sample is 45MPa, and tension fracture elongation rate is 390%, and heat decomposition temperature is 322 DEG C, is melted
Point is 200 DEG C.
Embodiment 9
The polyvinyl alcohol and 900g distilled water for weighing 90g are dissolved by heating at 95 DEG C, then by 5g alkylphenol-polyethenoxies
Ether phosphate (NP-4P), 5g APESs phosphate (NP-10P), 5g APES phosphates (NP-
15P) add and be uniformly mixed in solution, then pour into mixed solution in container, vacuum drying obtains sample at 60 DEG C,
Hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using thermal gravimetric analyzer and difference
Lose scanning calorimeter and test its heat decomposition temperature and fusing point respectively.
The tensile strength of gained film is 51MPa, and tension fracture elongation rate is 375%, and heat decomposition temperature is 308 DEG C, is melted
Point is 201 DEG C.
Embodiment 10
Weigh 90 parts of polyvinyl alcohol, 5 parts of APES phosphate (NP-4P), APES phosphorus
In 5 parts of acid esters (NP-10P), 5 parts of addition homogenizers of APES phosphate (NP-15P), it is sufficiently mixed
It is even, compound is made；Then compound is put into extruding pelletization in single screw extrusion machine, and thermoplastic polyvinyl alcohol composition is made,
Hot-forming preparation standard batten is carried out, tensile property test is carried out by GB-13022 standards, using thermal gravimetric analyzer and difference
Lose scanning calorimeter and test its heat decomposition temperature and fusing point respectively.Wherein extruder temperature is 205 DEG C, and screw speed is 100rpm,
Die temperature is 200 DEG C, and pelleter hauling speed is 10rpm.
The tensile strength of gained sample is 49MPa, and tension fracture elongation rate is 356%, and heat decomposition temperature is 305 DEG C, is melted
Point is 203 DEG C.
In order to prove to add phosphate compounds and be not added with the polyvinyl alcohol compositions product of phosphate compounds
The difference of mechanical properties, below spy enumerate two comparative examples.
Comparative example 1
Weigh 100 parts of polyvinyl alcohol to dissolve by heating at 95 DEG C with 3000 parts of distilled water, then pour into solution in container,
Vacuum drying obtains sample at 80 DEG C, carries out cutting preparation standard batten.Tensile property test is carried out by GB-13022 standards,
Its heat decomposition temperature and fusing point are tested using thermal gravimetric analyzer and mistake scanning calorimeter respectively.
The tensile strength of gained sample is 59MPa, and tension fracture elongation rate is 318%, and heat decomposition temperature is 240 DEG C, is melted
Point is 231 DEG C.
Comparative example 2
Weigh in 85 parts of polyvinyl alcohol, 15 parts of addition homogenizers of glycerine, at 80 DEG C, be sufficiently mixed uniform, system
Obtain compound；Then extruding pelletization in double screw extruder is added mixture into, hot-forming preparation standard batten is carried out, presses
GB-13022 standards carry out tensile property test, and its thermal decomposition is tested respectively using thermal gravimetric analyzer and mistake scanning calorimeter
Temperature and fusing point.Wherein extruder temperature is 230 DEG C, and screw speed is 100rpm, and die temperature is 220 DEG C, pelletizing machine travel speed
Spend for 10rpm.
The tensile strength of gained sample is 54MPa, and tension fracture elongation rate is 352%, and heat decomposition temperature is 236 DEG C, is melted
Point is 201 DEG C.
Polyvinyl alcohol compositions product obtained by the embodiment of the present invention and comparative example carries out the hot-forming or system of directly cutting out
Standby standard batten, tensile property test is carried out by GB-13022 standards, is surveyed using thermal gravimetric analyzer and mistake scanning calorimeter
Try its heat decomposition temperature, fusing point.Test result is shown in Table 1.
Table 1
| Project | Tensile strength/MPa | Elongation at break/% | Heat decomposition temperature/DEG C | Fusing point/DEG C |
| Embodiment 1 | 53 | 386 | 286 | 195 |
| Embodiment 2 | 50 | 362 | 302 | 204 |
| Embodiment 3 | 48 | 348 | 314 | 215 |
| Embodiment 4 | 52 | 364 | 283 | 198 |
| Embodiment 5 | 49 | 343 | 300 | 206 |
| Embodiment 6 | 47 | 328 | 311 | 218 |
| Embodiment 7 | 48 | 419 | 327 | 196 |
| Embodiment 8 | 45 | 403 | 322 | 200 |
| Embodiment 9 | 51 | 375 | 308 | 201 |
| Embodiment 10 | 49 | 356 | 305 | 203 |
| Comparative example 1 | 59 | 318 | 240 | 231 |
| Comparative example 2 | 54 | 352 | 236 | 201 |
Compared with comparative example 1, because embodiment 2 adds weight than APES (10) phosphate for 5%
NP-10P, PVA heat decomposition temperature improve 62 DEG C, and fusing point reduces 27 DEG C, and tensile strength and elongation at break change
Less.Compared with comparative example 1, embodiment 7 adds 10% APES (10) phosphate NP-10P, PVA heat
Decomposition temperature improves 87 DEG C, and fusing point reduces 35 DEG C, and tensile strength and elongation at break change are little.With comparative example 1
Compare, the phosphate of addition is more, its heat decomposition temperature improves more, fusing point reduces more, both differences are bigger, more have
Beneficial to melt-processed, while remain more excellent mechanical property.
Claims (6)
1. a kind of polyvinyl alcohol compositions of melt-processable, it is characterised in that said composition includes polyvinyl alcohol and phosphoric acid ester
Compound, the ratio of weight and number between polyvinyl alcohol and phosphate compounds is 70~99：30~1.
2. polyvinyl alcohol compositions according to claim 1, it is characterised in that the degree of polymerization of described polyvinyl alcohol is 500
~2400, alcoholysis degree is 85~100%.
3. polyvinyl alcohol compositions according to claim 1, it is characterised in that the structure of the phosphate compounds is led to
Formula is as follows：
In formula, R is C1~C30 alkyl chain, alkaryl chain or fatty alcohol alkyl chain, alkaryl chain, and M is oxirane (EO)
Or expoxy propane (PO), R1、R2It is 1~30 for H or M, n.
4. the preparation method of polyvinyl alcohol compositions according to claims 1 to 3, it is characterised in that：By polyvinyl alcohol with
Mixed material addition extruder, than being pre-mixed, is then extruded, will squeezed according to weight by phosphate compounds
The material pelletizing gone out, is made thermoplastic polyvinyl alcohol composition.
5. the preparation method of polyvinyl alcohol compositions according to claims 1 to 3, it is characterised in that：Polyvinyl alcohol is put
Enter and homogeneous solution is configured in distilled water, then the ratio of weight and number according to claim 1 weighs phosphate compounds and adds poly- second
It is agitated well mixed, dry in enolate solution；Then dried compound is put into extruder, directly extrusion is made
Grain, is made thermoplastic polyvinyl alcohol composition；Wherein extrusion temperature is 140~240 DEG C.
6. the purposes of the polyvinyl alcohol compositions according to any one of Claims 1 to 5, it is characterised in that the composition is used
In preparing fibre, film product, hollow container, tubing or sheet material.
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| CN201710419247.0A CN107163463B (en) | 2017-06-06 | 2017-06-06 | Polyvinyl alcohol composition capable of being melt-processed and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528817A (en) * | 2006-07-27 | 2009-09-09 | 日本合成化学工业株式会社 | Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate |
| CN101845185A (en) * | 2009-03-25 | 2010-09-29 | 刘建林 | PVA alloy capable of being processed with thermoplasticity method and manufacture technology thereof |
| CN103113698A (en) * | 2013-01-09 | 2013-05-22 | 湖南工业大学 | Plasticizer formula for hot melting process of partially alcoholized polyvinyl alcohol and process |
| CN105622828A (en) * | 2016-01-27 | 2016-06-01 | 浙江农林大学 | Drug-carrying polymer wood/bamboo modifier, and production and application methods thereof |
-
2017
- 2017-06-06 CN CN201710419247.0A patent/CN107163463B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528817A (en) * | 2006-07-27 | 2009-09-09 | 日本合成化学工业株式会社 | Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate |
| CN101845185A (en) * | 2009-03-25 | 2010-09-29 | 刘建林 | PVA alloy capable of being processed with thermoplasticity method and manufacture technology thereof |
| CN103113698A (en) * | 2013-01-09 | 2013-05-22 | 湖南工业大学 | Plasticizer formula for hot melting process of partially alcoholized polyvinyl alcohol and process |
| CN105622828A (en) * | 2016-01-27 | 2016-06-01 | 浙江农林大学 | Drug-carrying polymer wood/bamboo modifier, and production and application methods thereof |
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