CN103951919A - Polyvinyl alcohol composite master batch and preparation method thereof - Google Patents
Polyvinyl alcohol composite master batch and preparation method thereof Download PDFInfo
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- CN103951919A CN103951919A CN201410140344.2A CN201410140344A CN103951919A CN 103951919 A CN103951919 A CN 103951919A CN 201410140344 A CN201410140344 A CN 201410140344A CN 103951919 A CN103951919 A CN 103951919A
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Abstract
The invention discloses a polyvinyl alcohol composite master batch and a preparation method thereof. The polyvinyl alcohol composite master batch is a blend comprising polyvinyl alcohol, and polyhydroxyalkanoate; the weight content of the polyvinyl alcohol is 51-99%, and the weight content of the polyhydroxyalkanoate is 1-49%. The method comprises the following steps: well mixing polyvinyl alcohol powder with polyhydroxyalkanoate powder, adding deionized water, and well mixing to obtain a mixture; drying the mixture, injecting the mixture into a screw extruder with a heating device, melting at 175-185 DEG C for 4-8 min, performing melt extrusion and natural cooling to normal temperature, and cutting into particles by a pelletizer. The material is a novel environment friendly material, can degrade naturally after being used and discarded, and causes no environment burden; the material has significantly decreased melt viscosity at a relatively low temperature range and a wide shearing rate range, and has excellent thermoplastic processing performance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of polyvinyl alcohol composite master batch and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is a kind of water-soluble biological degradable macromolecule, has good machinery, physics, chemical property and film-forming properties, is widely used in the fields such as film, fiber, binding agent, paper making additive.But, in PVA main chain, containing a large amount of hydroxyls, the intermolecular and a large amount of hydrogen bonds of the interior formation of molecule, approach its fusing point and decomposition temperature, are difficult to carry out conventional thermoplastic processing.And conventional solution wet moulding, as solution casting film forming etc., need to experience dissolving and the drying process of resin, there is the shortcomings such as complex process, cost is high, productive rate is low, wastewater discharge is large.Although China is the production and consumption big country of PVA goods, the production technique of PVA still, taking traditional solution machine-shaping as main, is unfavorable for industry development.Therefore the thermoplastic of, realizing PVA is processed significant.
At present, the method for the known PVA of realization thermoplastic processing is to add the small-molecule substances such as water, alcohols, hexanolactam, reduces fusing point and the shear viscosity of PVA by plastification.As document [polymer science and engineering, 2008,24(5): 84-87] glycerine, polyoxyethylene glycol, hexanolactam etc. are made to Compositional type Plasticising system, with the PVA PVA-Plasticising system of making soluble in water, can effectively reduce melting index, reduce the fusing point of PVA, improved heat decomposition temperature, improved product appearance.Publication number is that the Chinese invention patent of 10313698A has proposed a kind of plasticizer formula and complete processing for the processing of PVA thermoplastic, realizes the thermoplastic processing of PVA.But itself is volatile under higher processing temperature for organic molecule softening agent, from goods, separates out, thereby affect the use properties of goods.In the alcamines properties-correcting agent plasticising PVA system of document [Chinese Plastics, 2003,17(2): 60-62] report, PVA plasticizing capacity is variation along with the increase of PVA alcoholysis degree.And document [plastics industry, 2002,30(1): 32-34] research of PVA plasticising is shown: the problem that exists long-term placement easily to separate out for PVA being carried out to the amides organic molecule of plasticising.Publication number is the production method that the Chinese patent of CN102391598A has been reported a kind of polyvinyl alcohol material, its technical characterstic is by softening agent plasticising PVA under the condition that has water to exist, under lower than polyvinyl alcohol decomposition temperature, carry out hot melt processing, but water is easily volatilization under comparatively high temps, usually work in-process produces bubble, can not realize stable and continuous and produce.
Obviously, the processing of the thermoplastic of PVA is technological difficulties and the research and development focus of this technical field.Current known technology is all carried out plasticising by add the small-molecule substance such as water, glycerine in PVA to it, bring thus softening agent residual, separate out, and produce the problem such as bubble, flaw in the thermoplastic course of processing.Therefore, the technology that urgently exploitation makes new advances is processed with the thermoplastic of realizing PVA, and avoids the variety of issue being brought by small molecules plasticising.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, a kind of polyvinyl alcohol composite master batch is provided.
Polyvinyl alcohol composite master batch of the present invention is blend, and this blend comprises polyvinyl alcohol, polyhydroxyalkanoate; Wherein the weight content of polyvinyl alcohol is 51～99 ﹪, and the weight content of polyhydroxyalkanoate is 1～49 ﹪, at 175～185 DEG C, 100s
-1under the condition of shearing rate, the apparent shear viscosity of polyvinyl alcohol composite master batch, lower than 20000Pas, has good thermoplastic processability;
As preferably, in polyvinyl alcohol composite master batch, the weight content of polyvinyl alcohol is 60～90 ﹪, and the weight content of polyhydroxyalkanoate is 10～40 ﹪, at 175～185 DEG C, 100s
-1under the condition of shearing rate, the apparent shear viscosity of polyvinyl alcohol composite master batch, lower than 10000Pas, has good thermoplastic processability.
Another object of the present invention is to provide the preparation method of above-mentioned polyvinyl alcohol composite master batch.
The inventive method comprises the following steps:
Step (1). pva powder and polyhydroxyalkanoate powder are carried out to physical mixed is even for the first time, then add deionized water to carry out physical mixed for the second time, after mixing, obtain compound; Wherein the weight ratio of pva powder and polyhydroxyalkanoate powder is 51:49～99:1, and the weight of deionized water is 0.5～1.5 ﹪ of pva powder and polyhydroxyalkanoate powder gross weight;
As preferably, the weight ratio of pva powder and polyhydroxyalkanoate powder is 6:4～9:1;
The equal particle diameter of number of described pva powder is 0.01～0.1mm, and mean polymerisation degree is 600～1800, and alcoholysis degree is 88 ﹪～99.8 ﹪ (mol/mol);
As preferably, the equal particle diameter of the number of pva powder is 0.01～0.055mm, and mean polymerisation degree is 600～1000, and alcoholysis degree is 88 ﹪～99.8 ﹪ (mol/mol);
The equal particle diameter of number of described polyhydroxyalkanoate powder is 0.01～0.1mm, has following chemical structure of general formula:
In formula: R
1, R
2independent is separately H, methyl CH
3or ethyl C
2h
5; M1, m2 are independently 1 or 2 separately; X, y are independently 0 or 200～20000 random natural number separately, and x, y are 0 when different.
As preferably, R in the chemical structure of general formula of described polyhydroxyalkanoate powder
1for methyl CH
3, m1 is 1, x is 200～20000 random natural number, y be within 0 o'clock, to be poly 3-hydroxy butyrate (P-3HB), the equal particle diameters of its number are 0.01～0.1mm, volume crystallinity is that 30～70 ﹪, weight-average molecular weight are 9～650,000;
As preferably, described polyhydroxyalkanoate powder R in general formula
1be within 0 o'clock, to be poly-4 hydroxybutyric acid ester (P-4HB) for H, m1 are 2, x is 200～20000 random natural number, y, the equal particle diameters of its number are 0.01～0.1mm, and volume crystallinity is that 30～70 ﹪, weight-average molecular weight are 9～650,000;
As preferably, described polyhydroxyalkanoate powder R in general formula
1for ethyl C
2h
5, m1 is 1, x is 200～20000 random natural number, y be within 0 o'clock, to be poly-3-hydroxyl valerate (P-3HV), the equal particle diameters of its number are 0.01～0.1mm, volume crystallinity is that 15～55 ﹪, weight-average molecular weight are 9～650,000;
As preferably, described polyhydroxyalkanoate powder R in general formula
1for methyl CH
3, R
2for H, m1 are 1, m2 is 2, x and y are poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters (P-3HB-4HB) while being 200～20000 random natural number, the equal particle diameter of its number is 0.01～0.1mm, volume crystallinity is that 10～50 ﹪, weight-average molecular weight are 9～750,000, and the molar content of 4 hydroxybutyric acid ester (P-4HB) is wherein 1～45 ﹪;
As preferably, described polyhydroxyalkanoate powder R in general formula
1for methyl CH
3, R
2for ethyl C
2h
5, m1 and m2 be 1, x and y are polyhydroxybutyrate-valeric acid copolyesters (PHBV) while being 200～20000 random natural number, the equal particle diameter of its number is 0.01～0.1mm, volume crystallinity is that 15～65 ﹪, weight-average molecular weight are 9～750,000, and the molar content of 3-hydroxyl valerate (P-3HV) is wherein 1～45 ﹪;
Step (2). the compound that step (1) is obtained vacuum-drying in 60～100 DEG C is constant to constant weight, removes excessive moisture;
Step (3). dried step (2) compound is injected to the screw extrusion press with heating unit, and the length-to-diameter ratio of screw rod is melting 4～8 minutes at 10～30,175～185 DEG C, melt extrudes and obtains melt extrusion;
Step (4). step (3) melt extrusion is naturally cooled to normal temperature in air, and tablets press pelletizing, prepares the particulate polyethylene alcohol composite master batch that can be used for thermoplastic processing.
Polyvinyl alcohol composite master batch of the present invention comprises and is biodegradable polyvinyl alcohol and polyhydroxyalkanoate component, is a kind of novel environmental friendly materials, use can natural degradation after discarded, environment is not caused to burden.This polyvinyl alcohol composite master batch has significantly reduced melt viscosity in relatively low temperature range and wider range of shear rate, has excellent thermoplastic processing characteristics.The present invention passes through great many of experiments, discovery only has in the time that the structural parameter of polyvinyl alcohol and polyhydroxyalkanoate (particle diameter, mean polymerisation degree, alcoholysis degree, chemical structure, molecular weight, degree of crystallinity, co-monomer content) meet specified conditions, could there is appropriate hydroxyl and interact in the two, make the original hydrogen bond of polyvinyl alcohol weakened, polyhydroxyalkanoate disperse phase deforms, is orientated simultaneously, thereby reduces the melt viscosity of compound system.This polyvinyl alcohol composite master batch has avoided ordinary method to add the small-molecule substance such as water, glycerine for realizing the processing of polyvinyl alcohol thermoplastic, solve small-molecule substance and in the course of processing, produced the problem such as separate out in bubble, use procedure, contributed to improve outward appearance homogeneity and the stability of goods.The present invention also proposes the preparation method of above-mentioned polyvinyl alcohol composite master batch, by physical mixed for the first time make pva powder and polyhydroxyalkanoate powder dispersed; Add appropriate water by physical mixed for the second time again, make pva powder surface that shallow-layer occur and dissolve, increase the binding property between pva powder and polyhydroxyalkanoate powder; Then control the temperature and time window that melt extrudes, guaranteeing that the homodisperse while of compound system effectively avoids the thermal destruction of polyvinyl alcohol.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.In embodiment, the apparent shear viscosity of polyvinyl alcohol composite master batch employing model is GOTTFERT
tM, the capillary rheometer determining of RHEO-TESTER2000.Pva powder in embodiment is in the temperature range of 175～185 DEG C and 100s
-1shearing rate under apparent shear viscosity all higher than 20000Pas, cannot melt extrude smoothly.
Embodiment 1:
The equal particle diameter of peeking is 90 kilograms of 0.01mm, mean polymerisation degree are 600, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 10 kilograms, 70 ﹪, weight-average molecular weight poly 3-hydroxy butyrate (P-3HB) powder that is 90,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 175 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9520,3730,510Pas, there is good thermoplastic processability.
Embodiment 2:
The equal particle diameter of peeking is 75 kilograms of 0.0325mm, mean polymerisation degree are 800, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.0325mm, volume crystallinity are that 25 kilograms, 50 ﹪, weight-average molecular weight poly 3-hydroxy butyrate (P-3HB) powder that is 370,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 180 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9600,3980,530Pas, there is good thermoplastic processability.
Embodiment 3:
The equal particle diameter of peeking is 60 kilograms of 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 40 kilograms, 30 ﹪, weight-average molecular weight poly 3-hydroxy butyrate (P-3HB) powder that is 650,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 8 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the conical double screw extruder that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9850,4160,550Pas, there is good thermoplastic processability.
Embodiment 4:
The equal particle diameter of peeking is 60 kilograms of 0.0325mm, mean polymerisation degree are 600, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 40 kilograms, 70 ﹪, weight-average molecular weight poly-4 hydroxybutyric acid ester (P-4HB) powder that is 370,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 175 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 8400,2550,405Pas, there is good thermoplastic processability.
Embodiment 5:
The equal particle diameter of peeking is 90 kilograms of 0.01mm, mean polymerisation degree are 800, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 10 kilograms, 50 ﹪, weight-average molecular weight poly-4 hydroxybutyric acid ester (P-4HB) powder that is 90,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the conical double screw extruder that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9650,4110,560Pas, there is good thermoplastic processability.
Embodiment 6:
The equal particle diameter of peeking is 75 kilograms of 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.0325mm, volume crystallinity are that 25 kilograms, 30 ﹪, weight-average molecular weight poly-4 hydroxybutyric acid ester (P-4HB) powder that is 650,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 10 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 180 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9800,4230,575Pas, there is good thermoplastic processability.
Embodiment 7:
The equal particle diameter of peeking is 60 kilograms of 0.055mm, mean polymerisation degree are 600, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 40 kilograms, 15 ﹪, weight-average molecular weight poly-3-hydroxyl valerate (P-3HV) powder that is 90,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 8 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 175 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7420,2300,382Pas, there is good thermoplastic processability
Embodiment 8:
The equal particle diameter of peeking is 75 kilograms of 0.0325mm, mean polymerisation degree are 800, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.0325mm, volume crystallinity are that 25 kilograms, 35 ﹪, weight-average molecular weight poly-3-hydroxyl valerate (P-3HV) powder that is 650,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 180 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9510,3860,525Pas, there is good thermoplastic processability.
Embodiment 9:
The equal particle diameter of peeking is 90 kilograms of 0.01mm, mean polymerisation degree are 1000, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 10 kilograms, 55 ﹪, weight-average molecular weight poly-3-hydroxyl valerate (P-3HV) powder that is 370,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the twin screw extruder that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9850,4260,580Pas, there is good thermoplastic processability.
Embodiment 10:
The equal particle diameter of peeking is 90 kilograms of 0.055mm, mean polymerisation degree are 600, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 10 kilograms, 30 ﹪, weight-average molecular weight are 750,000,4 hydroxybutyric acid ester (P-4HB) molar content is 23 ﹪ poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters (P-3HB-4HB) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 10 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7250,2260,370Pas, there is good thermoplastic processability.Embodiment 11:
The equal particle diameter of peeking is 60 kilograms of 0.01mm, mean polymerisation degree are 800, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 40 kilograms, 50 ﹪, weight-average molecular weight are 90,000,4 hydroxybutyric acid ester (P-4HB) molar content is 1 ﹪ poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters (P-3HB-4HB) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 5 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the conical double screw extruder that screw slenderness ratio is 20, at 175 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7080,2100,353Pas, there is good thermoplastic processability.Embodiment 12:
The equal particle diameter of peeking is 75 kilograms of 0.0325mm, mean polymerisation degree are 1000, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.0325mm, volume crystallinity are that 25 kilograms, 10 ﹪, weight-average molecular weight are 420,000,4 hydroxybutyric acid ester (P-4HB) molar content is 45 ﹪ poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters (P-3HB-4HB) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 8 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 180 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7200,2210,360Pas, there is good thermoplastic processability.Embodiment 13:
The equal particle diameter of peeking is 75 kilograms of 0.01mm, mean polymerisation degree are 600, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.0325mm, volume crystallinity are that 25 kilograms, 40 ﹪, weight-average molecular weight are 90,000,3-hydroxyl valerate (P-3HV) molar content is 23 ﹪ polyhydroxybutyrate-valeric acid copolyesters (PHBV) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 8 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the conical double screw extruder that screw slenderness ratio is 10, at 175 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7430,2290,378Pas, there is good thermoplastic processability.
Embodiment 14:
The equal particle diameter of peeking is 90 kilograms of 0.0325mm, mean polymerisation degree are 800, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 10 kilograms, 15 ﹪, weight-average molecular weight are 420,000,3-hydroxyl valerate (P-3HV) molar content is 45 ﹪ polyhydroxybutyrate-valeric acid copolyesters (PHBV) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 185 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s-in temperature
1under apparent shear viscosity be respectively 7500,2320,390Pas, there is good thermoplastic processability.
Embodiment 15:
The equal particle diameter of peeking is 60 kilograms of 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 40 kilograms, 65 ﹪, weight-average molecular weight are 750,000,3-hydroxyl valerate (P-3HV) molar content is 1 ﹪ polyhydroxybutyrate-valeric acid copolyesters (PHBV) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 180 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 7540,2400,400Pas, there is good thermoplastic processability.
Embodiment 16:
The equal particle diameter of peeking is 75 kilograms of 0.01mm, mean polymerisation degree are 1200, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.055mm, volume crystallinity are that 25 kilograms, 55 ﹪, weight-average molecular weight poly-3-hydroxyl valerate (P-3HV) powder that is 370,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 180 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9600,4100,550Pas, there is good thermoplastic processability.
Embodiment 17:
The equal particle diameter of peeking is 51 kilograms of 0.1mm, mean polymerisation degree are 1800, alcoholysis degree is 93.9 ﹪ (mol/mol) pva powders is that 0.1mm, volume crystallinity are that 49 kilograms, 70 ﹪, weight-average molecular weight poly-4 hydroxybutyric acid ester (P-4HB) powder that is 650,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 8850,2920,448Pas, there is good thermoplastic processability.
Embodiment 18:
The equal particle diameter of peeking is 99 kilograms of 0.055mm, mean polymerisation degree are 600, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.01mm, volume crystallinity are that 1 kilogram, 65 ﹪, weight-average molecular weight are 90,000,3-hydroxyl valerate (P-3HV) molar content is 1 ﹪ polyhydroxybutyrate-valeric acid copolyesters (PHBV) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 10 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the twin screw extruder that screw slenderness ratio is 20, at 175 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 10030,3110,452Pas, there is good thermoplastic processability.
Embodiment 19:
The equal particle diameter of peeking is 60 kilograms of 0.055mm, mean polymerisation degree are 1000, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.1mm, volume crystallinity are that 40 kilograms, 55 ﹪, weight-average molecular weight poly-3-hydroxyl valerate (P-3HV) powder that is 370,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 0.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 80 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 175 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 175 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 8600,2730,425Pas, there is good thermoplastic processability.
Embodiment 20:
The equal particle diameter of peeking is 90 kilograms of 0.0325mm, mean polymerisation degree are 800, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.1mm, volume crystallinity are that 10 kilograms, 40 ﹪, weight-average molecular weight are 500,000,3-hydroxyl valerate (P-3HV) molar content is 45 ﹪ polyhydroxybutyrate-valeric acid copolyesters (PHBV) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 20, at 185 DEG C, melt extrude, it is 4 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9000,3020,460Pas, there is good thermoplastic processability.
Embodiment 21:
The equal particle diameter of peeking is 75 kilograms of 0.0325mm, mean polymerisation degree are 1000, alcoholysis degree is 88 ﹪ (mol/mol) pva powders is that 0.1mm, volume crystallinity are that 25 kilograms, 10 ﹪, weight-average molecular weight are 420,000,4 hydroxybutyric acid ester (P-4HB) molar content is 45 ﹪ poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters (P-3HB-4HB) powder carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 8 hours at 60 DEG C, remove excessive moisture; Dried compound is injected to the single screw extrusion machine that screw slenderness ratio is 30, at 180 DEG C, melt extrude, it is 6 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 180 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 6750,1900,310Pas, there is good thermoplastic processability.
Embodiment 22:
The equal particle diameter of peeking is 60 kilograms of 0.01mm, mean polymerisation degree are 800, alcoholysis degree is 99.8 ﹪ (mol/mol) pva powders is that 0.1mm, volume crystallinity are that 40 kilograms, 50 ﹪, weight-average molecular weight poly 3-hydroxy butyrate (P-3HB) powder that is 90,000 carries out physical mixed for the first time in homogenizer with the equal particle diameters of number, mixing temperature is normal temperature, and the time is 3～5 minutes; Then add 1.5 kg water, carry out physical mixed for the second time, mixing temperature is normal temperature, and the time is 3～5 minutes; By compound vacuum-drying 6 hours at 100 DEG C, remove excessive moisture; Dried compound is injected to the conical double screw extruder that screw slenderness ratio is 10, at 185 DEG C, melt extrude, it is 8 minutes that adjustment screw speed makes the fusion time of compound; By melt extrusion naturally cooling in air, tablets press pelletizing, prepares oyster white, ganoid particulate polyethylene alcohol composite master batch.Through capillary rheometer determining, this masterbatch is that 185 DEG C, shearing rate are 100,1000,10000s in temperature
-1under apparent shear viscosity be respectively 9200,3360,475Pas, there is good thermoplastic processability.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (10)
1. a polyvinyl alcohol composite master batch, is blend, it is characterized in that this blend comprises polyvinyl alcohol, polyhydroxyalkanoate; Wherein the weight content of polyvinyl alcohol is 51～99 ﹪, and the weight content of polyhydroxyalkanoate is 1～49 ﹪, at 175～185 DEG C, 100s
-1under the condition of shearing rate, the apparent shear viscosity of polyvinyl alcohol composite master batch is lower than 20000Pas;
The mean polymerisation degree of polyvinyl alcohol is 600～1800, and alcoholysis degree is 88 ﹪～99.8 ﹪, and unit is mol/mol;
Polyhydroxyalkanoate has following chemical structure of general formula:
In formula: R
1, R
2independent is separately H, methyl CH
3or ethyl C
2h
5; M1, m2 are independently 1 or 2 separately; X, y are independently 0 or 200～20000 random natural number separately, and x, y are 0 when different.
2. a kind of polyvinyl alcohol composite master batch as claimed in claim 1, the weight content that it is characterized in that polyvinyl alcohol in polyvinyl alcohol composite master batch is 60～90 ﹪, the weight content of polyhydroxyalkanoate is 10～40 ﹪, at 175～185 DEG C, 100sw
1under the condition of shearing rate, the apparent shear viscosity of polyvinyl alcohol composite master batch is lower than 10000Pas;
The mean polymerisation degree of polyvinyl alcohol is 600～1000, and alcoholysis degree is 88 ﹪～99.8 ﹪, and unit is mol/mol.
3. the method for preparation a kind of polyvinyl alcohol composite master batch as claimed in claim 1, is characterized in that the method comprises the following steps:
Step (1). pva powder and polyhydroxyalkanoate powder are carried out to physical mixed is even for the first time, then add deionized water to carry out physical mixed for the second time, after mixing, obtain compound; Wherein the weight ratio of polyvinyl alcohol and polyhydroxyalkanoate is 51:49～99:1, and the weight of deionized water is 0.5～1.5 ﹪ of polyvinyl alcohol and polyhydroxyalkanoate gross weight;
The equal particle diameter of number of described polyvinyl alcohol is 0.01～0.1mm, and mean polymerisation degree is 600～1800, and alcoholysis degree is 88 ﹪～99.8 ﹪, and unit is mol/mol;
The equal particle diameter of number of described polyhydroxyalkanoate is 0.01～0.1mm, has following chemical structure of general formula:
In formula: R
1, R
2independent is separately H, methyl CH
3or ethyl C
2h
5; M1, m2 are independently 1 or 2 separately; X, y are independently 0 or 200～20000 random natural number separately, and x, y are 0 when different;
Step (2). the compound that step (1) is obtained vacuum-drying in 60～100 DEG C is constant to constant weight, removes excessive moisture;
Step (3). dried step (2) compound is injected to the screw extrusion press with heating unit, and the length-to-diameter ratio of screw rod is melting 4～8 minutes at 10～30,175～185 DEG C, melt extrudes and obtains melt extrusion;
Step (4). step (3) melt extrusion is naturally cooled to normal temperature in air, and tablets press pelletizing, prepares the particulate polyethylene alcohol composite master batch that can be used for thermoplastic processing.
4. the preparation method of a kind of polyvinyl alcohol composite master batch as claimed in claim 3, the weight ratio that it is characterized in that polyvinyl alcohol and polyhydroxyalkanoate is 6:4～9:1.
5. the preparation method of a kind of polyvinyl alcohol composite master batch as claimed in claim 3, is characterized in that the equal particle diameter of number of polyvinyl alcohol is 0.01～0.055mm, and mean polymerisation degree is 600～1000, and alcoholysis degree is 88 ﹪～99.8 ﹪, and unit is mol/mol.
6. the preparation method of a kind of polyvinyl alcohol composite master batch as described in a kind of polyvinyl alcohol composite master batch and the claim 3,4 as described in claim 1,2, is characterized in that R in the chemical structure of general formula of polyhydroxyalkanoate
1for methyl CH
3, m1 is 1, x is 200～20000 random natural number, y be within 0 o'clock, to be poly 3-hydroxy butyrate, the equal particle diameters of its number are 0.01～0.1mm, volume crystallinity is that 30～70 ﹪, weight-average molecular weight are 9～650,000.
7. the preparation method of a kind of polyvinyl alcohol composite master batch as described in a kind of polyvinyl alcohol composite master batch and the claim 3,4 as described in claim 1,2, is characterized in that polyhydroxyalkanoate R in general formula
1be within 0 o'clock, to be poly-4 hydroxybutyric acid ester for H, m1 are 2, x is 200～20000 random natural number, y, the equal particle diameters of its number are 0.01～0.1mm, and volume crystallinity is that 30～70 ﹪, weight-average molecular weight are 9～650,000.
8. the preparation method of a kind of polyvinyl alcohol composite master batch as described in a kind of polyvinyl alcohol composite master batch and the claim 3,4 as described in claim 1,2, is characterized in that polyhydroxyalkanoate R in general formula
1for ethyl C
2h
5, m1 is 1, x is 200～20000 random natural number, y be within 0 o'clock, to be poly-3-hydroxyl valerate, the equal particle diameters of its number are 0.01～0.1mm, volume crystallinity is that 15～55 ﹪, weight-average molecular weight are 9～650,000.
9. the preparation method of a kind of polyvinyl alcohol composite master batch as described in a kind of polyvinyl alcohol composite master batch and the claim 3,4 as described in claim 1,2, is characterized in that polyhydroxyalkanoate R in general formula
1for methyl CH
3, R
2for H, m1 are 1, m2 is 2, x and y are poly-3-hydroxybutyrate-4 hydroxybutyric acid copolyesters while being 200～20000 random natural number, the equal particle diameter of its number is 0.01～0.1mm, volume crystallinity is that 10～50 ﹪, weight-average molecular weight are 9～750,000, and the molar content of 4 hydroxybutyric acid ester is wherein 1～45 ﹪.
10. the preparation method of a kind of polyvinyl alcohol composite master batch as described in a kind of polyvinyl alcohol composite master batch and the claim 3,4 as described in claim 1,2, is characterized in that polyhydroxyalkanoate R in general formula
1for methyl CH
3, R
2for ethyl C
2h
5, m1 and m2 be 1, x and y are polyhydroxybutyrate-valeric acid copolyesters while being 200～20000 random natural number, the equal particle diameter of its number is 0.01～0.1mm, volume crystallinity is that 15～65 ﹪, weight-average molecular weight are 9～750,000, and the molar content of 3-hydroxyl valerate is wherein 1～45 ﹪.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371290A (en) * | 2014-11-14 | 2015-02-25 | 苏州蔻美新材料有限公司 | Environment-friendly composite biological high polymer material and preparation method thereof |
| CN109370130A (en) * | 2018-10-31 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of preparation method of highly concentrated low polyethylene alcohol system's melt and its film |
| CN109517308A (en) * | 2018-10-31 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of preparation method of polaroid polyethenol series melt and its film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06287393A (en) * | 1993-04-01 | 1994-10-11 | Kuraray Co Ltd | Polyvinyl alcohol resin composition |
| CN1444445A (en) * | 2000-06-09 | 2003-09-24 | 宝洁公司 | Agricultural items and methods comprising biodegradable copolymers |
| CN103205076A (en) * | 2013-04-15 | 2013-07-17 | 四川大学 | Thermoplastic polyvinyl alcohol-polylactic acid blending material and preparation method thereof |
-
2014
- 2014-04-09 CN CN201410140344.2A patent/CN103951919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06287393A (en) * | 1993-04-01 | 1994-10-11 | Kuraray Co Ltd | Polyvinyl alcohol resin composition |
| CN1444445A (en) * | 2000-06-09 | 2003-09-24 | 宝洁公司 | Agricultural items and methods comprising biodegradable copolymers |
| CN103205076A (en) * | 2013-04-15 | 2013-07-17 | 四川大学 | Thermoplastic polyvinyl alcohol-polylactic acid blending material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汪劲波等: ""聚乙二醇改性的热塑性淀粉的结构与性能"", 《化学工业与工程技术》, vol. 27, no. 2, 30 April 2006 (2006-04-30), pages 20 - 23 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371290A (en) * | 2014-11-14 | 2015-02-25 | 苏州蔻美新材料有限公司 | Environment-friendly composite biological high polymer material and preparation method thereof |
| CN109370130A (en) * | 2018-10-31 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of preparation method of highly concentrated low polyethylene alcohol system's melt and its film |
| CN109517308A (en) * | 2018-10-31 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of preparation method of polaroid polyethenol series melt and its film |
| CN109370130B (en) * | 2018-10-31 | 2021-07-02 | 中国石油化工股份有限公司 | Preparation method of high-concentration low-viscosity polyvinyl alcohol melt and film thereof |
| CN109517308B (en) * | 2018-10-31 | 2021-07-16 | 中国石油化工股份有限公司 | Polyvinyl alcohol melt for polaroid and preparation method of film thereof |
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