CN106189010B - A kind of polyvinyl alcohol film of blow molding and preparation method thereof - Google Patents

A kind of polyvinyl alcohol film of blow molding and preparation method thereof Download PDF

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CN106189010B
CN106189010B CN201510233821.4A CN201510233821A CN106189010B CN 106189010 B CN106189010 B CN 106189010B CN 201510233821 A CN201510233821 A CN 201510233821A CN 106189010 B CN106189010 B CN 106189010B
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polyvinyl alcohol
parts
film
temperature
melt
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CN106189010A (en
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李莉
黎园
王琪
雷德松
吴春林
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Sichuan University
China Petrochemical Corp
Sinopec Sichuan Vinylon Works
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Sichuan University
China Petrochemical Corp
Sinopec Sichuan Vinylon Works
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Abstract

The present invention provides a kind of polyvinyl alcohol films, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterized by: tensile strength >=20MPa of the polyvinyl alcohol film, the melt-processable polyvinyl alcohol resin includes a effective amount of polyvinyl alcohol, plasticizer, soft water and processing aid, the degree of polymerization (DP) of the polyvinyl alcohol is 1000-3500, 72 (mol) %≤alcoholysis degree (DH) <, 99.9 (mol) %, the plasticizer is glycerine, polyethylene glycol, at least one of two tricaprylate of triethylene glycol, the processing aid is talcum powder, silica, oleamide, at least one of saturated aliphatic dicarboxylic acids ester.Present invention process is simple, and equipment investment is few, and occupied area is few, can be blow molded the water-soluble film of room temperature, medium temperature, high temperature.Bilayer film mainly is prepared, is directly prepared into various water-soluble sacks, is used for low and middle-end packaging applications field.Pesticide, chemical products inner packing lining bag are such as done, packaging bag, refuse bag etc. wash in hospital.

Description

A kind of polyvinyl alcohol film of blow molding and preparation method thereof
Technical field
The present invention relates to a kind of polyvinyl alcohol films of blow molding, and in particular to the polyethylene in low and middle-end packaging applications field Alcohol film.
Background technique
PVA film preparation method has solution casting method and melting extrusion blowing, is referred to as wet process and dry method.Solution stream It is longer to prolong method process flow, product quality is not easy to control, and membrane rate is low, and energy consumption is high, and equipment investment is big, prepared PVA film Weatherability is bad, and when winter humidity is low, the easy embrittlement of film is Texturized；When summer humidity is larger, films tacky, size shakiness It is fixed.
Melting extrusion film forming is that PVA and some processing aid mixing granulations are then carried out the dry method of melting extrusion film forming Filming technology.The simple process, membrane rate is high, and low energy consumption, and occupied area is small, institute's made membrane good weatherability, dimensionally stable.
Since polyvinyl alcohol is polyhydroxy structure, there are intermolecular and intramolecular strong hydrogen bonding active forces, so that melting temperature With decomposition temperature very close to, it is difficult to carry out thermoplastic processing.Thus, PVA film available on the market is substantially all using solution Casting films made of the tape casting technique.
Summary of the invention
The purpose of the present invention is to provide a kind of using high-quality polyvinyl alcohol film made from blow molding process.
The purpose of the present invention is what is realized by following measures:
A kind of polyvinyl alcohol film, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: described poly- Tensile strength >=20MPa of vinyl alcohol film, the melt-processable polyvinyl alcohol resin are by a effective amount of polyvinyl alcohol, plasticising Agent, soft water and processing aid composition, the degree of polymerization (DP) of the polyvinyl alcohol are 1000-3500,72 (mol) %≤alcoholysis degrees (DH) < 99.9 (mol) %, the plasticizer are at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, institute Stating processing aid is at least one of talcum powder, silica, oleamide, saturated aliphatic dicarboxylic acids ester.
Above-mentioned polyvinyl alcohol is common polythene alcohol or carboxy-modified polyvinyl alcohol.
Above-mentioned polyvinyl alcohol film, using common polythene alcohol as raw material, polyvinyl alcohol film oxygen transmission rate < 20cm3/(m2* * 0.1MPa for 24 hours), the degree of polymerization (DP) of the polyvinyl alcohol is 1000-2400,72 (mol) %≤alcoholysis degree (DH) < 99.9 (mol) %, the processing aid are talcum powder, silica, oleamide, at least one in saturated aliphatic dicarboxylic acids ester Kind.
Above-mentioned polyvinyl alcohol film, using carboxy-modified polyvinyl alcohol as raw material, polyvinyl alcohol film oxygen transmission rate < 30cm3/ (m2* * 0.1MPa for 24 hours), the carboxy-modified polyvinyl alcohol is total to by vinyl acetate monomer and the unsaturated monomer containing carboxyl Obtained after poly- through alcoholysis, alcoholysis degree be 80.0-99.9 (mol) %, the degree of polymerization is 1000~3500, carboxyl-content for 0.1~ 20mol%；The processing aid is talcum powder, silica, oleamide, at least one in saturated aliphatic dicarboxylic acids ester Kind.Unsaturated monomer in carboxy-modified polyvinyl alcohol of the present invention containing carboxyl refers to the insatiable hunger containing more than one COOH group With carboxylic acid, esters of unsaturated carboxylic acids or unsaturated acid anhydride, such as itaconic acid, acrylic acid, maleic acid, butyl acrylate, clothing health Acid anhydrides, maleic anhydride etc..
Above-mentioned saturated aliphatic dicarboxylic acids ester is by containing 2-30 C atom, the fatty acid of 1-5 COOH group and containing 1-10 A C atom, made of the fatty acid of 1-5 OH group, which is commercially available production Product, such as the trade mark of Hangzhou Jin Cheng auxiliary agent Co., Ltd production are the saturated aliphatic dicarboxylic acids ester of G32, G36, G60 etc..On State glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, talcum powder, silica, oleamide, saturated aliphatic dicarboxylic acids Ester is known, commercial product.
Plasticizer of the present invention effectively reduces the melt processing temperature of PVA；On the one hand soft water of the present invention plays the work of plasticizer With another aspect plays swelling action, PVA molecule is allowed preferably to absorb plasticizer and processing aid.Processing aid and PVA of the present invention Compatibility is good.Above-mentioned melt-processable polyvinyl alcohol resin melting temperature, which is effectively reduced, can be used for melting thermoplastic is processed into Type, decomposition temperature are also improved, significantly improve melt-processable polyvinyl alcohol resin quality；Meanwhile it is entire fusible plus Work polyvinyl alcohol resin system lubricity is good, and placement is not easy the moisture absorption, adhesion.
In order to further improve the melt-processable of melt-processable polyvinyl alcohol resin of the present invention, improve its quality, Preferably, above-mentioned resin by 50-85 parts of above-mentioned polyvinyl alcohol, 5-40 parts of above-mentioned plasticizer, 5-35 parts of above-mentioned soft water and 0.1-15 parts of above-mentioned processing aid compositions.
In order to further improve the decomposition temperature of obtained thermoplasticity carboxy-modified polyvinyl alcohol resin, to improve it Quality, while improving its weatherability, above-mentioned melt-processable polyvinyl alcohol resin be with a effective amount of polyvinyl alcohol, plasticizer, Soft water, processing aid and crosslinking agent for raw material be made, the crosslinking agent be calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, At least one of borax.
In order to preferably improve the quality of melt-processable polyvinyl alcohol resin, it is highly preferred that above-mentioned resin is with 50-85 parts Above-mentioned polyvinyl alcohol, 5-40 parts of above-mentioned plasticizer, 5-35 parts of above-mentioned soft water, 0.1-15 parts of above-mentioned processing aids and on 0.1-5 parts of crosslinking agents are stated to be made for raw material.
Above-mentioned melt-processable polyvinyl alcohol resin can be any shape, as graininess, cylindrical, cone shape, Square figure, cuboid-type, sheet, disc-shaped, S shape, V-arrangement, hollow circuit cylinder figure, the hollow cone bodily form, hollow square figure, At least any shape in hollow cuboid-type.
The above-mentioned preferred diameter of melt-processable polyvinyl alcohol resin is 0.5-15mm, the cylindrical body of high 0.5-15mm.
Melt-processable polyvinyl alcohol resin of the present invention is by way of blow molding by melt-processable polyvinyl alcohol resin Preparation film forming, mainly for the preparation of bilayer film, is directly prepared into various water-soluble sacks, is used for low and middle-end packaging applications field.Such as Pesticide, chemical products inner packing lining bag are done, packaging bag, refuse bag etc. wash in hospital.Specifically:
The preparation method of the polyvinyl alcohol film of above-mentioned Blown Film, comprising the following steps:
(1) by 50-85 parts of polymer, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, with any suitable Sequence addition is uniformly mixed under stirring and is warming up to 30-90 DEG C, holding 1/6-10 hours；Or 50-85 parts are polymerize Object, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, 0.1-5 parts of crosslinking agents are added with random order, are being stirred It mixes and 30-90 DEG C is uniformly mixed and be warming up under state, kept for 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, normal pressure or pressurized conditions Lower melting extrusion, is cooled to 20-40 DEG C, and melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding.
(3) resin described in (2) step is heated to molten condition, melting temperature is 130~190 DEG C, is blown through Screw Extrusion It is moulded into film, thermoplastic processing is carried out and water-soluble polyvinyl alcohol film is made.
When containing crosslinking agent in blending constituent described in above-mentioned (1) step, also adds 0.1-5 parts of crosslinking agents and be uniformly mixed.
The hybrid mode of material preferably uses agitating mode to mix in above-mentioned (1) step.
The preferred single screw extrusion machine of screw extruder in above-mentioned (2) step.
Screw extruder is divided into feeding part and screw rod melting extrusion part in above-mentioned (2) step, wherein feeding part Feeding bin use with blender feeding bin.
Above-mentioned melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host adds Hot-zone is at least Three-section type heating, and melting temperature is 130~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
It is water-soluble that the water-soluble polyvinyl alcohol film of the water-soluble polyvinyl alcohol film of high temperature, medium temperature, room temperature can be obtained in the present invention respectively Polyvinyl alcohol film.
The water-soluble polyvinyl alcohol film of room temperature is prepared, melt-processable polyvinyl alcohol resin is by a effective amount of conventional polyvinyl Alcohol, plasticizer, soft water and processing aid composition, wherein the degree of polymerization (DP) of polyvinyl alcohol be 1000-2400,72 (mol) %≤ 90 (mol) % of alcoholysis degree (DH) <.Preferably, the plasticizer be the glycerine of mass ratio 2-5: 0-3: 1-4, polyethylene glycol, Two tricaprylate of triethylene glycol composition, the processing aid are talcum powder, silica, the oil of mass ratio 1-3: 2-5: 0-2: 1-6 Sour amide, saturated aliphatic dicarboxylic acids ester composition.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, wrapped in raw material Include crosslinking agent.Alternatively, melt-processable polyvinyl alcohol resin by a effective amount of carboxy-modified polyvinyl alcohol, plasticizer, soft water and Processing aid composition, the carboxy-modified polyvinyl alcohol is used to be obtained with after the copolymerization of itaconic acid monomer through alcoholysis by vinyl acetate monomer , alcoholysis degree is 80.0-90.0 (mol) %, the degree of polymerization is 1000~3500, carboxyl-content is 0.1~20mol%；It is above-mentioned Plasticizer is glycerine, polyethylene glycol, two tricaprylate of the triethylene glycol composition of mass ratio 1-2: 0-4: 3-5, the processing aid For the talcum powder of mass ratio 0-2: 0-3: 2-4: 1-3, silica, oleamide, saturated aliphatic dicarboxylic acids ester composition.In order to The quality of thermoplastic polyvinyl alcohol resin is preferably improved, includes crosslinking agent in raw material, above-mentioned crosslinking agent is mass ratio 0-3: 0-2: 0-4: 0-5: 3-5: 2-4 calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid and borax composition.
Prepare the water-soluble polyvinyl alcohol film of medium temperature: its melt-processable polyvinyl alcohol resin is by a effective amount of conventional polyvinyl Alcohol, plasticizer, soft water and processing aid composition, wherein the degree of polymerization (DP) of the polyvinyl alcohol is 1000-2400,90 (mol) 95 (mol) % of %≤alcoholysis degree (DH) <.Preferably, the plasticizer is the third the three of mass ratio 0-1: 4-4.5: 2-3 Alcohol, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are the cunning of mass ratio 1-3: 0-1: 2.5-3.5: 2-4 Mountain flour, silica, oleamide, saturated aliphatic dicarboxylic acids ester composition.In order to preferably improve thermoplastic polyvinyl alcohol tree The quality of rouge, includes crosslinking agent in raw material, crosslinking agent be preferably mass ratio 0-1: 1-2: 0-2: 0-3: 3-4: 1-2 calcium acetate, Zinc acetate, copper chloride, zinc chloride, boric acid and borax composition.Alternatively, melt-processable polyvinyl alcohol resin is by a effective amount of carboxyl Modified polyvinylalcohol, plasticizer, soft water and processing aid composition, the carboxy-modified polyvinyl alcohol are used by vinyl acetate monomer It obtaining with after the copolymerization of itaconic acid monomer through alcoholysis, 90.0 (mol) % < alcoholysis degree <, 95 (mol) %, the degree of polymerization be 1000~ 3500, carboxyl-content is 0.1~20mol%；Above-mentioned plasticizer is glycerine, the polyethylene glycol, three of mass ratio 2-3: 3-4: 4-6 Two tricaprylate of glycol composition, the processing aid are talcum powder, silica, the oleic acid of mass ratio 4-5: 0-6: 3-5: 2-4 Amide, saturated aliphatic dicarboxylic acids ester composition.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, include in raw material Crosslinking agent, the crosslinking agent are calcium acetate, zinc acetate, the copper chloride, chlorination of mass ratio 3-5: 1-2: 0-3: 1-2: 4-6: 5-7 Zinc, boric acid and borax composition.
The water-soluble polyvinyl alcohol film of high temperature is prepared, melt-processable polyvinyl alcohol resin is by a effective amount of polyvinyl alcohol, increasing Agent, soft water and processing aid composition are moulded, wherein the degree of polymerization (DP) of the polyvinyl alcohol is 1000-2400, alcoholysis degree (DH) is 95 (mol) %-99.9 (mol) %.Preferably, the plasticizer be the glycerine of mass ratio 0-2: 5-6: 1-2, polyethylene glycol, Two tricaprylate of triethylene glycol composition, the processing aid are talcum powder, silica, the oil of mass ratio 4-5: 0-3: 4-6: 0-3 Sour amide, saturated aliphatic dicarboxylic acids ester composition.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, wrapped in raw material Crosslinking agent is included, crosslinking agent is preferably calcium acetate, zinc acetate, copper chloride, the chlorine of mass ratio 2-3: 0-0.5: 3-4: 0-1: 1-2: 3-4 Change zinc, boric acid and borax composition.Or melt-processable polyvinyl alcohol resin is by a effective amount of carboxy-modified polyvinyl alcohol, plasticising Agent, soft water and processing aid composition, the carboxy-modified polyvinyl alcohol is used to be copolymerized by vinyl acetate monomer and itaconic acid monomer Obtained by alcoholysis, alcoholysis degree 95.0-99.9mol%, the degree of polymerization are 1000~3500, carboxyl-content be 0.1~ 20mol%；Above-mentioned plasticizer is glycerine, polyethylene glycol, two tricaprylate of the triethylene glycol composition of mass ratio 0-4: 2-3: 4-6, The processing aid is talcum powder, silica, oleamide, the representative examples of saturated aliphatic dicarboxyl of mass ratio 1-2: 1-2: 0-4: 1-3 Acid esters composition.It include crosslinking agent in raw material, the crosslinking agent is to preferably improve the quality of thermoplastic polyvinyl alcohol resin Calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid and the borax composition of mass ratio 0-1: 2-3: 1-2: 0-3: 1-3: 2-4.
Beneficial effect
1. present invention process is simple, equipment investment is few, and occupied area is few, can be blow molded the water-soluble film of room temperature, medium temperature, high temperature. Bilayer film mainly is prepared, is directly prepared into various water-soluble sacks, is used for low and middle-end packaging applications field.Such as do pesticide, chemical industry produces Product inner packing serves as a contrast bag, and packaging bag, refuse bag etc. wash in hospital.
2. polyvinyl alcohol film tensile strength >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed) of the invention, thin Film thickness >=30 μm, oxygen transmission rate < 30cm3/(m2* * 0.1MPa for 24 hours), light transmittance >=70%, have it is water-disintegrable and can biology drop Xie Xing will not generate " white pollution " in the environment.
3. the present invention realizes the thermoplastic processing of PVA by the method for physical blending, and it is prepared for that room temperature is water-soluble, medium temperature A series of melt-processable polyvinyl alcohol resin products water-soluble, high temperature is water-soluble, high-temperature water contain intermingle with the melting temperature of vinyl alcohol resin Degree is reduced to 120-200 DEG C, dissolves in 80-90 DEG C of water, and melt index is 2-8g/10min (160 DEG C/2.16~10kg)； Normal-temperature water contains intermingle with vinyl alcohol resin melting temperature and is reduced to 120-180 DEG C, melt index be 2-8g/10min (140 DEG C/2.16~ 10kg), conventional polyvinyl alcohol resin water solution temperature is 15-40 DEG C, 5-30 DEG C of water solution temperature of carboxy-modified polyvinyl alcohol resin；In Warm water contains intermingle with vinyl alcohol resin melting temperature and is reduced to 120-200 DEG C, dissolves in 40-60 DEG C of water, melt index 2-8g/ 10min (150 DEG C/2.16~10kg).High-temperature water contains intermingle with 80-100 DEG C of PVA film water solution temperature made from vinyl alcohol resin, decomposes Temperature is increased to 300 DEG C -350 DEG C；PVA film water solution temperature made from the water-soluble conventional polyvinyl alcohol resin of room temperature be 15-30 DEG C, point Solution temperature is increased to 260 DEG C -350 DEG C, and carboxy-modified polyvinyl alcohol film water solubility temperature is 5-30 DEG C, and decomposition temperature is increased to 300 ℃-350℃；PVA film water solution temperature made from medium temperature water-soluble polyvinyl alcohol resin is 40-60 DEG C, and decomposition temperature is increased to 300 ℃-350℃。
4. melt-processable polyvinyl alcohol resin product appearance of the invention is colorless and transparent, non-yellowing, and thermoplastic processing mistake Cheng Zhongwu poisonous and harmful substance generates, and processing fluidity is excellent, good moldability；Excellent in mechanical performance for following process.This The film strength for inventing preparation is high, and intensity reaches 45-120MPa after drying；Resin lubrication is good, nonhygroscopic, adhesion, puts simultaneously Set 1 year appearance, color will not change；Non-toxic of the present invention can degrade under certain conditions, be conducive to environmental protection. Adjustment thermoplastic processing technique can prepare the water-soluble film of PVA of different field demand.
The present invention relates to test method it is as follows:
1. the test of melting temperature and decomposition temperature: being characterized using heat analysis (DSC) curve, tested in nitrogen atmosphere, risen Warm rate: 10 DEG C/min, Range of measuring temp: -250 DEG C of room temperature.
2. the test of melt index: according to the thermoplastic polyvinyl alcohol resin flow behavior of the different PVA trades mark, using melting Index Instrument, under certain temperature, constant pressure, measurement plastic melt flows through the mass value of standard capillary, unit g/ in 10min 10min.This test method set temperature: 140 DEG C~180 DEG C；Pressure: 2.16kg~10kg.
3. film stretching strength determination: being carried out with reference to standard GB/T 13022-91 stretched plastic film method for testing performance Test.
4. film oxygen transmission rate is tested: referring to national standard GB/T1038-2000 plastic film and thin slice gas-premeable test side Method pressure differential method.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein to be, the present embodiment is served only for Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field Some nonessential modifications and adaptations are made to the present invention according to above content, still fall within protection scope of the present invention.Following reality It applies in example, unless otherwise, all % and number are all as unit of mass percentage, mass weight.
Embodiment 1: by 50 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 72.0 (mol) %), 40 parts of polyethylene glycol, 20 Part soft water, 0.1 part of oleamide are uniformly mixed under stirring, are heated at a temperature of 30 DEG C, are stopped while stirring after ten minutes Only heat.Then material is added in the feed bin with stirring, is delivered to material in screw extruder automatically using screw rod, protected Hold 120 DEG C of extruder temperature, melting extrusion in atmospheric conditions, then material is cooled to 20 DEG C, it is made through pelleter pelletizing moulding Thermoplastic polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the side being blow molded through Screw Extrusion Formula, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion Blown Film is squeezed out using single screw rod Inflation film manufacturing machine, draw ratio are 22~28, and screw host heating zone is at least Three-section type heating, and melting temperature is 130~190 DEG C, mould Mouth gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplastic polyvinyl alcohol resin is 260 DEG C, and resin is colorless and transparent, non-yellowing, melting temperature 140 DEG C, melt index 5g/10min (140 DEG C/2.16~10kg), resin is graininess, and water solubility temperature is 20-30 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 31 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 2: by 55 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 80.0 (mol) %), 37 parts of glycerine, 18 parts Soft water, 0.5 part of silica mixing, are uniformly mixed under stirring, heat while stirring at a temperature of 40 DEG C, after 30 minutes Stop heating.Then material is added in the feed bin with stirring, material is delivered to by single screw extrusion machine using screw rod automatically In, 130 DEG C of extruder temperature of holding, the melting extrusion under 0.01MPa (gauge pressure) pressure condition, then material is cooled to 30 DEG C, warp Thermoplastic polyvinyl alcohol resin is made in pelleter pelletizing moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, The mode being blow molded through Screw Extrusion, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion is blow molded into Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature Degree is 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 265 DEG C, 130 DEG C of melting temperature, melt index 4g/10min (140 DEG C/2.16~ 10kg), resin is diameter 2.0mm, and the cylindrical body of high 0.5mm, water solubility temperature is 15-30 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 36 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)
Embodiment 3: by 40 parts of conventional polyvinyl alcohols (degree of polymerization 1500, alcoholysis degree 88.0 (mol) %), 32 parts of triethylene glycols two Tricaprylate, 17 parts of soft water, 1 part of talcum powder mixing, are uniformly mixed under stirring, add while stirring at 50 °C Heat stops heating after sixty minutes.Then material is added in the feed bin with stirring, is delivered to material automatically using single screw rod In single screw extrusion machine, 130 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 35 DEG C, through cutting Thermoplastic polyvinyl alcohol resin is made in grain machine-cut grain moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, is passed through The mode of Screw Extrusion blow molding, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion Blown Film It is that inflation film manufacturing machine is squeezed out using single screw rod, draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature It is 150~190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 270 DEG C, 145 DEG C of melting temperature, melt index 5g/10min (140 DEG C/2.16~ 10kg), resin is positive cube shape, and water solubility temperature is 20-35 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 32 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)
Embodiment 4: it is by 65 parts of conventional polyvinyl alcohols (degree of polymerization 2000, alcoholysis degree 86.0 (mol) %), 28 parts of mass ratioes The silica that 1: 1 glycerine and polyethylene glycol mixture, 35 parts of soft water, 2 parts of mass ratioes are 2: 1 is blended with oleamide Object mixing, material is uniformly mixed, and is heated 2 hours in 60 DEG C of temperature, is then stopped heating.Then material addition single screw rod is squeezed Out in machine, 130 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 35 DEG C, through pelleter pelletizing Thermoplastic polyvinyl alcohol resin is made in moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through Screw Extrusion The mode of blow molding, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion Blown Film is using single Screw Extrusion inflation film manufacturing machine, draw ratio are 22~28, and screw host heating zone is at least Three-section type heating, melting temperature is 130~ 190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 272 DEG C, 150 DEG C of melting temperature, melt index 5g/10min (140 DEG C/2.16~ 10kg), resin is hollow cylinder shape, and water solubility temperature is 25-40 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 39 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 5: by 50 parts of conventional polyvinyl alcohols (degree of polymerization 1200, alcoholysis degree 78.0 (mol) %), 25 parts of triethylene glycols two Tricaprylate, 10 parts of soft water, 5 parts of oleamide mixing, are uniformly mixed under stirring, add while stirring at a temperature of 60 DEG C Heat stops heating after 3 hours.Then material is added in the feed bin with stirring, is delivered to material automatically using twin-screw In single screw extrusion machine, 140 DEG C of extruder temperature of holding, the melting extrusion under 0.05MPa pressure condition, then material is cooled to 40 DEG C, thermoplastic polyvinyl alcohol resin is made through pelleter pelletizing moulding.Gained thermoplastic polyvinyl alcohol resin is heated to melting State, the mode being blow molded through Screw Extrusion, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion is blown Being moulded into film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melts Melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is according to extruded velocity tune Section.
The decomposition temperature of gained resin be 280 DEG C, 160 DEG C of melting temperature, melt index 6g/10min (140 DEG C/2.16~ 10kg), resin is the cylindrical shape of diameter 3mm high 3mm.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 37 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)
Embodiment 6: being 3.5 by 75 parts of polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 80.0 (mol) %), 17 parts of mass ratioes: 1.5: 2.5 glycerine, mixture, 8 parts of soft water, the 10 parts of mass ratioes of two tricaprylate of triethylene glycol and polyethylene glycol are 2: 3.5 Talcum powder mixed with the mixture of silica, under stirring be uniformly mixed, heated while stirring at a temperature of 90 DEG C, Stop heating after 4 hours.Then material is added in the feed bin with stirring, material is delivered to using twin-screw by single spiral shell automatically In bar extruder, 150 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 30 DEG C, through pelleter Thermoplastic polyvinyl alcohol resin is made in pelletizing moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through screw rod The mode of extrusion-blown modling, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion Blown Film is to adopt Inflation film manufacturing machine is squeezed out with single screw rod, draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 275 DEG C, 170 DEG C of melting temperature, melt index 7g/10min (140 DEG C/2.16~ 10kg), resin is the cylindrical shape of diameter 4mm high 6mm.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 33 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 7: by 80 parts of conventional polyvinyl alcohols (degree of polymerization 1800, alcoholysis degree 85.0 (mol) %), 10 parts of glycerine, 5 Part soft water, 15 parts of saturated aliphatic dicarboxylic acids ester G32 mixing, are uniformly mixed under stirring, stir below in 80 DEG C of temperature Side heating, stops heating after 5 hours.Then material is added in the feed bin with stirring, is conveyed material automatically using screw rod Into single screw extrusion machine, 160 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 25 DEG C, warp Thermoplastic polyvinyl alcohol resin is made in pelleter pelletizing moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, The mode being blow molded through Screw Extrusion, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion is blow molded into Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature Degree is 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 270 DEG C, 130 DEG C of melting temperature, melt index 8g/10min (140 DEG C/2.16~ 10kg), resin is the cylindrical shape of diameter 2mm high 15mm.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 31 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 8: being 5: 4 by 85 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 82.0 (mol) %), 5 parts of mass ratioes Talcum powder, silica and the saturated fat that two tricaprylate of glycerine and triethylene glycol, 14 parts of soft water, 6 parts of mass ratioes are 3: 5: 1 Race dicarboxylic ester G36,2 parts of crosslinking agent calcium acetate mixing, are uniformly mixed under stirring, add while stirring at a temperature of 90 DEG C Heat stops heating after 6 hours.Then material is added in the feed bin with stirring, is delivered to material automatically using twin-screw In single screw extrusion machine, 180 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 30 DEG C, through cutting Thermoplastic polyvinyl alcohol resin is made in grain machine-cut grain moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, is passed through The mode of Screw Extrusion blow molding, progress thermoplastic processing are made normal-temperature water and contain intermingle with alcohol film.The melting extrusion Blown Film It is that inflation film manufacturing machine is squeezed out using single screw rod, draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature It is 130~190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 290 DEG C, 180 DEG C of melting temperature, melt index 5g/10min (140 DEG C/2.16~ 10kg), resin is the cylindrical shape of diameter 10mm high 5mm.
The decomposition temperature of resulting polyvinyl alcohol film is 260-350 DEG C, and water solution temperature is 15-30 DEG C, 34 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 9: by 85 parts of carboxy-modified polyvinyl alcohols, (carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and clothing Obtained after the copolymerization of health acid monomers through alcoholysis, alcoholysis degree is 80 (mol) %, the degree of polymerization 3500, carboxyl-content 20mol%), 20 parts of polyethylene glycol, 20 parts of glycerine, 20 parts of soft water, 15 parts of saturated fatty acid race dicarboxylic ester G60 are mixed under stirring Uniformly, it is heated while stirring at a temperature of 30 DEG C, stops heating after 10h.Then material is added in the feed bin with stirring, is adopted Material is delivered in screw extruder automatically with screw rod, 200 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then Material is cooled to 40 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained thermoplasticity Polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, and progress thermoplastic processing is made normal-temperature water and contains intermingle with second Enol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host adds Hot-zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 320 DEG C, and resin is colorless and transparent, non-yellowing, 125 DEG C of melting temperature, melt index 5.5g/10min (140 DEG C/2.16~10kg), resin is graininess, and water solubility temperature is 5-20℃。
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 5-30 DEG C, 33 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 10: by 52 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Itaconic anhydride copolymerization after obtained through alcoholysis, alcoholysis degree be 90 (mol) %, the degree of polymerization 1000, carboxyl-content 9mol%), 5 Part glycerine, 7 parts of soft water, 0.1 part of silica, 0.1 part of oleamide mixing, are uniformly mixed, at 90 DEG C under stirring At a temperature of heat while stirring, after ten minutes stop heating.Then material is added in the feed bin with stirring, it will using screw rod Material is delivered in single screw extrusion machine automatically, is kept for 120 DEG C of extruder temperature, melted under 0.01MPa (gauge pressure) pressure condition It squeezes out, then material is cooled to 20 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained Thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and normal-temperature water is made Contain intermingle with alcohol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, screw rod Host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, screw speed 10 ~20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 300 DEG C, and 140 DEG C of melting temperature, melting refers to Number 2.5g/10min (140 DEG C/2.16~10kg), resin are diameter 2.0mm, the cylindrical body of high 0.5mm, water solubility temperature 5- 15℃。
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 5-30 DEG C, 35 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 11: by 65 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Obtained after acrylic acid copolymer through alcoholysis, alcoholysis degree is 85 (mol) %, the degree of polymerization 2000, carboxyl-content 0.1mol%), 28 parts of two tricaprylates of triethylene glycol, 13 parts of soft water, 5 parts of talcum powder, 5 parts of saturated fatty acid race dicarboxylic ester G36 mixing, are being stirred It is uniformly mixed under state, is heated while stirring at a temperature of 60 DEG C, stop heating after 2h.Then material is added with stirring In feed bin, material is delivered in single screw extrusion machine using single screw rod automatically, is kept for 150 DEG C of extruder temperature, in condition of normal pressure Lower melting extrusion, then material is cooled to 30 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding. Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion carries out thermoplastic processing and is made Normal-temperature water contains intermingle with alcohol film.The melting extrusion Blown Film be using single screw rod squeeze out inflation film manufacturing machine, draw ratio be 22~ 28, screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, screw rod 10~20rpm of revolving speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 350 DEG C, and 170 DEG C of melting temperature, melting refers to Number 4g/10min (140 DEG C/2.16~10kg), square shape, water solubility temperature are 20-30 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 5-30 DEG C, 37 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 12: by 85 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with It is obtained after butyl acrylate copolymerization through alcoholysis, alcoholysis degree is 88 (mol) %, the degree of polymerization 2500, and carboxyl-content is 3mol%), 30 parts of mass ratioes are 1: 4 two tricaprylate of glycerine and triethylene glycol, 8 parts of soft water, 12 parts of mass ratioes are 2: 3: 1 Talcum powder, silica and saturated aliphatic dicarboxylic acids ester G32, the zinc chloride of 5 parts of mass ratioes 4: 1 and boric acid are under stirring It is uniformly mixed, is heated while stirring at a temperature of 80 DEG C, stop heating after 1 hour.Then the material with stirring is added in material In storehouse, material is delivered in single screw extrusion machine using twin-screw automatically, is kept for 140 DEG C of extruder temperature, in atmospheric conditions Melting extrusion, then material is cooled to 30 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.It will Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and is made often Warm water contains intermingle with alcohol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, Screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw rod turns 10~20rpm of speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 330 DEG C, and 130 DEG C of melting temperature, melting refers to Number 6g/10min (140 DEG C/2.16~10kg), resin are the cylindrical shape of diameter 10mm high 5mm.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 5-30 DEG C, 32 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 13: 80 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 90.0 (mol) %), 36 parts of triethylene glycols two are different Caprylate, 20 parts of soft water, 2.5 parts of oleamides, 2 parts of talcum powder under stirring be uniformly mixed, stirred below in 60 DEG C of temperature Side heating is mixed, stops heating after 5h.Then material is added in the feed bin with stirring, is delivered to material automatically using screw rod In screw extruder, 160 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 30 DEG C, through pelletizing Graininess melt-processable polyvinyl alcohol resin is made in machine-cut grain moulding.Gained thermoplastic polyvinyl alcohol resin is heated to melting State, the mode being blow molded through Screw Extrusion carry out thermoplastic processing and water-soluble polyvinyl alcohol film are made.The melting extrusion is blow molded into Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature Degree is 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin is 300 DEG C, colorless and transparent, non-yellowing, 150 DEG C of melting temperature, melt index 6.5g/ 10min (150 DEG C/2.16~10kg), resin are graininess, and water solubility temperature is 45-55 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 32 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 14: by 50 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 94.0 (mol) %), 5 parts of polyethylene glycol, 5 parts Soft water, 0.1 part of silica mixing, are uniformly mixed under stirring, heat at a temperature of 30 DEG C, stop while stirring after 9h Heating.Then material is added in the feed bin with stirring, is delivered to material in single screw extrusion machine automatically using screw rod, protected 200 DEG C of screw rod temperature are held, the melting extrusion under 0.01MPa (gauge pressure) pressure condition, then material is cooled to 40 DEG C, through pelletizing machine-cut Melt-processable polyvinyl alcohol resin is made in grain moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through spiral shell The mode of bar extrusion-blown modling carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.The melting extrusion Blown Film is to use Single screw rod squeezes out inflation film manufacturing machine, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature 150 ~190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 260 DEG C, 130 DEG C of melting temperature, melt index 4g/10min (150 DEG C/2.16~ 10kg), resin is diameter 2.0mm, and the cylindrical body of high 0.5mm, water solubility temperature is 42-47 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 40 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 15: by 85 parts of conventional polyvinyl alcohols (degree of polymerization 2200, alcoholysis degree 93.0 (mol) %), 40 parts of glycerine, 30 parts of soft water, 15 parts of saturated aliphatic dicarboxylic acids ester G36 are uniformly mixed, and are heated 10 minutes in 90 DEG C of temperature, are then stopped heating. Then material is added in single screw extrusion machine, is kept for 120 DEG C of extruder temperature, melting extrusion in atmospheric conditions, then by material 20 DEG C are cooled to, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained thermoplastic polyvinyl alcohol tree Rouge is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.It is described molten Melting extrusion-blown modling film forming is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least three sections Formula heating, melting temperature are 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed according to Extruded velocity is adjusted.
The decomposition temperature of gained resin be 310 DEG C, 130 DEG C of melting temperature, melt index 7g/10min (150 DEG C/2.16~ 10kg), resin is hollow cylinder shape, and water solubility temperature is 48-58 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 35 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 16: being 1: 2 by 65 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 92.0 (mol) %), 25 parts of mass ratioes Two tricaprylate of glycerine and triethylene glycol, 15 parts of soft water, the silica that 10 parts of mass ratioes are 1: 3 and oleamide, 3 parts of friendships Join the mixing of agent borax, be uniformly mixed under stirring, heated while stirring at a temperature of 80 DEG C, stops heating after 2 hours.It connects By material be added with stirring feed bin in, material is delivered in single screw extrusion machine automatically using twin-screw, keep spiral shell 150 DEG C of bar temperature, melting extrusion in atmospheric conditions, then material is cooled to 35 DEG C, it is made fusible through pelleter pelletizing moulding Melt processing polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the side being blow molded through Screw Extrusion Formula carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.The melting extrusion Blown Film is to squeeze out blown film using single screw rod Machine, draw ratio are 22~28, and screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, die orifice seam Gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 290 DEG C, 170 DEG C of melting temperature, melt index 5g/10min (150 DEG C/2.16~ 10kg), the cylindrical shape of diameter 15mm high 15mm.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 38 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 17: by 70 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with It is obtained after the copolymerization of itaconic acid monomer through alcoholysis, alcoholysis degree is 92 (mol) %, the degree of polymerization 2200, and carboxyl-content is 12mol%), 28 parts of two tricaprylates of triethylene glycol, 2 parts of glycerine, 15 parts of soft water, 5 parts of saturated fatty acid race dicarboxylic ester G32,2 Part oleamide is uniformly mixed under stirring, is heated while stirring at a temperature of 44 DEG C, stops heating after 3h.Then by object Material is added in the feed bin with stirring, is delivered to material in screw extruder automatically using screw rod, keeps extruder temperature 135 DEG C, melting extrusion in atmospheric conditions, then material is cooled to 25 DEG C, it is carboxy-modified that thermoplasticity is made through pelleter pelletizing moulding Polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion carries out Medium temperature water-soluble polyvinyl alcohol film is made in thermoplastic processing.The melting extrusion Blown Film is to squeeze out inflation film manufacturing machine using single screw rod, Draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is small In 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 340 DEG C, colorless and transparent, non-yellowing, melting 125 DEG C of temperature, melt index 6.5g/10min (150 DEG C/2.16~10kg), resin is graininess, water solubility temperature 52-60 ℃。
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 36 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 18: by 80 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Obtained after itaconic anhydride copolymerization through alcoholysis, alcoholysis degree is 94 (mol) %, the degree of polymerization 3500, carboxyl-content 17mol%), 10 parts of glycerine, 16 parts of polyethylene glycol, 18 parts of soft water, 5 parts of silica, 9 parts of oleamide mixing, mix under stirring Uniformly, it is heated while stirring at a temperature of 90 DEG C, stops heating after 30 minutes.Then the feed bin with stirring is added in material It is interior, material is delivered in single screw extrusion machine automatically using screw rod, is kept for 200 DEG C of extruder temperature, is pressed in 0.01MPa (gauge pressure) Melting extrusion under the conditions of power, then material is cooled to 40 DEG C, the carboxy-modified polyethylene of thermoplasticity is made through pelleter pelletizing moulding Alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion carries out thermoplastic and adds Medium temperature water-soluble polyvinyl alcohol film is made in work.The melting extrusion Blown Film is to squeeze out inflation film manufacturing machine, draw ratio using single screw rod It is 22~28, screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 305 DEG C, and 156 DEG C of melting temperature, melting refers to Number 3.5g/10min (150 DEG C/2.16~10kg), water solubility temperature are 40-48 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 34 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 19: by 55 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with It is obtained after butyl acrylate copolymerization through alcoholysis, alcoholysis degree is 93 (mol) %, the degree of polymerization 2800, and carboxyl-content is 0.5mol%), 7 parts of two tricaprylates of triethylene glycol, 8 parts of soft water, 0.8 part of silica, 0.2 part of oleamide mixing, are being stirred It is uniformly mixed under state, is heated while stirring at a temperature of 35 DEG C, stop heating after 6h.Then material is added with stirring In feed bin, material is delivered in single screw extrusion machine using single screw rod automatically, is kept for 180 DEG C of extruder temperature, in condition of normal pressure Lower melting extrusion, then material is cooled to 20 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding. Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion carries out thermoplastic processing and is made Normal-temperature water contains intermingle with alcohol film.The melting extrusion Blown Film be using single screw rod squeeze out inflation film manufacturing machine, draw ratio be 22~ 28, screw host heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, screw rod 10~20rpm of revolving speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 320 DEG C, and 160 DEG C of melting temperature, melting refers to Number 5g/10min (150 DEG C/2.16~10kg), resin are positive cube shape, and water solubility temperature is 45-55 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 30 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 20: by 63 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Obtained after acrylic acid copolymer through alcoholysis, alcoholysis degree be 91 (mol) %, the degree of polymerization 1500, carboxyl-content 6mol%), 22 Talcum powder that the glycerine and polyethylene glycol, 11 parts of soft water, 5 parts of mass ratioes that part mass ratio is 1: 1 are 2: 3: 5, silica and Calcium acetate, zinc chloride and the boric acid mixing that oleamide, 5 parts of mass ratioes are 3: 1: 4, are uniformly mixed, 60 under stirring It is heated while stirring at a temperature of DEG C, stops heating after 2.6 hours.Then material is added in the feed bin with stirring, using double Material is delivered in single screw extrusion machine by screw rod automatically, 160 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then Material is cooled to 40 DEG C, thermoplasticity carboxy-modified polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained thermoplasticity Polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and the water-soluble poly- second of medium temperature is made Enol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host adds Hot-zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained thermoplasticity carboxy-modified polyvinyl alcohol resin is 310 DEG C, and 160 DEG C of melting temperature, melting refers to Number 7g/10min (150 DEG C/2.16~10kg).
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 40-60 DEG C, 36 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 21: 50 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 95.0 (mol) %), 6 parts of triethylene glycols two are different pungent Acid esters, 5 parts of soft water, 0.1 part of saturated aliphatic dicarboxylic acids ester G32 are uniformly mixed under stirring, are stirred below in 90 DEG C of temperature Side heating is mixed, stops heating after 7h.Then material is added in the feed bin with stirring, is delivered to material automatically using screw rod In screw extruder, 200 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 40 DEG C, through pelletizing Graininess melt-processable polyvinyl alcohol resin is made in machine-cut grain moulding.Gained thermoplastic polyvinyl alcohol resin is heated to melting State, the mode being blow molded through Screw Extrusion carry out thermoplastic processing and water-soluble polyvinyl alcohol film are made.The melting extrusion is blow molded into Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least Three-section type heating, melting temperature Degree is 130~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin is 320 DEG C, colorless and transparent, non-yellowing, 180 DEG C of melting temperature, melt index 5g/ 10min (160 DEG C/2.16~10kg), resin are graininess, and water solubility temperature is 60-68 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film be 300-350 DEG C, water solution temperature be 80-100 DEG C, 36 μm of thickness, Tensile strength >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 22: by 85 parts of polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 97.0 (mol) %), 20 parts of polyethylene glycol, 20 Part glycerine, 20 parts of soft water, 10 parts of silica, 5 parts of oleamides mixing, are uniformly mixed, in 30 DEG C of temperature under stirring It is heated while stirring under degree, stops heating after 10h.Then material is added in the feed bin with stirring, using screw rod by material Automatically it is delivered in single screw extrusion machine, 120 DEG C of screw rod temperature of holding, the melting extrusion under 0.01MPa (gauge pressure) pressure condition, then Material is cooled to 20 DEG C, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained thermoplastic poly second Enol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made. The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host heating zone is at least For Three-section type heating, melting temperature is 130~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.Traction speed Degree is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 350 DEG C, 120 DEG C of melting temperature, melt index 4g/10min (160 DEG C/2.16~ 10kg), resin is diameter 2.0mm, and the cylindrical body of high 0.5mm, water solubility temperature is 90-100 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film be 300-350 DEG C, water solution temperature be 80-100 DEG C, 35 μm of thickness, Tensile strength >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 23: by 70 parts of conventional polyvinyl alcohols (degree of polymerization 1000, alcoholysis degree 99.9 (mol) %), 30 parts of poly- second two Alcohol, 16 parts of soft water, 7 parts of saturated aliphatic dicarboxylic acids ester G36,3 parts of silica are uniformly mixed, and heat 2h in 55 DEG C of temperature, so Stop heating afterwards.Then material is added in single screw extrusion machine, is kept for 145 DEG C of extruder temperature, melting is squeezed in atmospheric conditions Out, then by material 25 DEG C are cooled to, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding.By gained thermoplasticity Polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and water-soluble polyvinyl alcohol is made Film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, screw host heating zone At least Three-section type heating, melting temperature are 130~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.It leads Draw speed to be adjusted according to extruded velocity.
The decomposition temperature of gained resin be 260 DEG C, 165 DEG C of melting temperature, melt index 7g/10min (160 DEG C/2.16~ 10kg), resin is hollow cylinder shape, and water solubility temperature is 70-80 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film be 300-350 DEG C, water solution temperature be 80-100 DEG C, 32 μm of thickness, Tensile strength >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 24: being 5: 1 by 60 parts of polyvinyl alcohol (degree of polymerization 1500, alcoholysis degree 96.0 (mol) %), 30 parts of mass ratioes Two tricaprylate of polyethylene glycol and triethylene glycol, 13 parts of soft water, the talcum powder and oleamide, 1.5 parts that 7 parts of mass ratioes are 1: 1 The boric acid and copper chloride of mass ratio 1: 2 are uniformly mixed under stirring, are heated while stirring at a temperature of 68 DEG C, 4.5 hours Stop heating afterwards.Then material is added in the feed bin with stirring, material is delivered to by single screw rod using twin-screw automatically and is squeezed Out in machine, 136 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 25 DEG C, through pelleter pelletizing Melt-processable polyvinyl alcohol resin is made in moulding.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through screw rod The mode of extrusion-blown modling carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.The melting extrusion Blown Film is using single Screw Extrusion inflation film manufacturing machine, draw ratio are 22~28, and screw host heating zone is at least Three-section type heating, melting temperature is 130~ 190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 315 DEG C, 150 DEG C of melting temperature, melt index 6.5g/10min (160 DEG C/2.16 ~10kg), resin is the cylindrical shape of diameter 2mm high 3mm.
The decomposition temperature of resulting polyvinyl alcohol film be 300-350 DEG C, water solution temperature be 80-100 DEG C, 33 μm of thickness, Tensile strength >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 20cm3/(m2*24h*0.1MPa)。
Embodiment 25: by 60 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Obtained after the copolymerization of itaconic acid monomer through alcoholysis, alcoholysis degree 95mol%, the degree of polymerization 1600, carboxyl-content 10mol%), 8 parts of polyethylene glycol, 2 parts of two tricaprylates of triethylene glycol, 9 parts of soft water, 2 parts of oleamides are uniformly mixed under stirring, 90 It is heated while stirring at a temperature of DEG C, stops heating after 10min.Then material is added in the feed bin with stirring, using screw rod Material is delivered in screw extruder automatically, is kept for 200 DEG C of extruder temperature, melting extrusion in atmospheric conditions, then by material 40 DEG C are cooled to, the carboxy-modified high-temperature water of thermoplasticity is made through pelleter pelletizing moulding and contains intermingle with vinyl alcohol resin.By gained thermoplastic Property polyvinyl alcohol resin be heated to molten condition, the mode being blow molded through Screw Extrusion carries out thermoplastic processing and normal-temperature water is made contains intermingle with Alcohol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, screw host Heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin is 300 DEG C, colorless and transparent, non-yellowing, 130 DEG C of melting temperature, melt index 3g/ 10min (160 DEG C/2.16~10kg), resin are graininess, and water solubility temperature is 80-85 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 80-90 DEG C, 35 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 26: by 70 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Itaconic anhydride copolymerization after obtained through alcoholysis, alcoholysis degree 99mol%, the degree of polymerization 2000, carboxyl-content 12mol%), 18 Part polyethylene glycol, 15 parts of soft water, 8 parts of oleamides mixing, are uniformly mixed, at a temperature of 30 DEG C while stirring under stirring Heating stops heating after 6 minutes.Then material is added in the feed bin with stirring, is delivered to material automatically using screw rod In single screw extrusion machine, 120 DEG C of extruder temperature of holding, the melting extrusion under 0.01MPa (gauge pressure) pressure condition, then material is cold But to 20 DEG C, the carboxy-modified high-temperature water of thermoplasticity is made through pelleter pelletizing moulding and contains intermingle with vinyl alcohol resin.By gained thermoplasticity Polyvinyl alcohol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, and progress thermoplastic processing is made normal-temperature water and contains intermingle with second Enol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and screw host adds Hot-zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 310 DEG C, 140 DEG C of melting temperature, melt index 5g/10min (160 DEG C/2.16~ 10kg), water solubility temperature is 85-88 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 80-90 DEG C, 38 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 27: by 85 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with Obtained after acrylic acid copolymer through alcoholysis, alcoholysis degree 98mol%, the degree of polymerization 3500, carboxyl-content 2mol%), 40 parts Two tricaprylate of triethylene glycol, 20 parts of soft water, 13 parts of silica, 2 parts of oleamides are uniformly mixed, 50 under stirring It is heated while stirring at a temperature of DEG C, stops heating after 3h.Then material is added in the feed bin with stirring, it will using single screw rod Material is delivered in single screw extrusion machine automatically, is kept for 170 DEG C of extruder temperature, melting extrusion in atmospheric conditions, then by material 30 DEG C are cooled to, the carboxy-modified high-temperature water of thermoplasticity is made through pelleter pelletizing moulding and contains intermingle with vinyl alcohol resin.By gained thermoplastic Property polyvinyl alcohol resin be heated to molten condition, the mode being blow molded through Screw Extrusion carries out thermoplastic processing and high-temperature water is made contains intermingle with Alcohol film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, screw host Heating zone is at least Three-section type heating, and melting temperature is 150~190 DEG C, and die gap is less than 1.0mm, and screw speed 10~ 20rpm.Hauling speed is adjusted according to extruded velocity.
The decomposition temperature of gained resin be 350 DEG C, 180 DEG C of melting temperature, melt index 6g/10min (160 DEG C/2.16~ 10kg), water solubility temperature is 85-90 DEG C.
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 80-90 DEG C, 35 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。
Embodiment 28: by 65 parts of carboxy-modified polyvinyl alcohols (carboxy-modified polyvinyl alcohol be by vinyl acetate monomer with It is obtained after butyl acrylate copolymerization through alcoholysis, alcoholysis degree 99.9mol%, the degree of polymerization 1200, carboxyl-content is 20mol%), talcum powder, silica and representative examples of saturated aliphatic two that 5 parts of glycerine, 16 parts of soft water, 10 parts of mass ratioes are 1: 1: 3 Carboxylate G36, the boric acid of 3 parts of mass ratioes 1: 2 and zinc acetate mixing, are uniformly mixed under stirring, following in 80 DEG C of temperature Side heating is stirred, stops heating after 1 hour.Then by material be added with stirring feed bin in, using twin-screw by material from It is dynamic to be delivered in single screw extrusion machine, 140 DEG C of extruder temperature of holding, melting extrusion in atmospheric conditions, then material is cooled to 40 DEG C, the carboxy-modified high-temperature water of thermoplasticity is made through pelleter pelletizing moulding and contains intermingle with vinyl alcohol resin.By gained thermoplastic poly second Enol resin is heated to molten condition, the mode being blow molded through Screw Extrusion, carries out thermoplastic processing and high temperature water-soluble polyvinyl alcohol is made Film.The melting extrusion Blown Film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, screw host heating zone At least Three-section type heating, melting temperature are 150~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.It leads Draw speed to be adjusted according to extruded velocity.
The decomposition temperature of gained resin be 330 DEG C, 125 DEG C of melting temperature, melt index 6g/10min (160 DEG C/2.16~ 10kg)。
The decomposition temperature of resulting polyvinyl alcohol film is 300-350 DEG C, and water solution temperature is 80-90 DEG C, 32 μm of thickness, is drawn Stretch intensity >=20MPa (23 DEG C, 50%RH, 100mm/min tensile speed), elongation at break 100%-300%, light transmittance 70.0% or more, oxygen transmission rate < 30cm3/(m2*24h*0.1MPa)。

Claims (26)

1. a kind of polyvinyl alcohol film, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: the poly- second Tensile strength>=20MPa of enol film, polyvinyl alcohol film oxygen transmission rate<, the melt-processable polyvinyl alcohol Resin is made of 50-85 parts of common polythene alcohol, 5-40 parts of plasticizer, 5-35 parts of soft water and 0.1-15 parts of processing aids, with Parts by weight meter；The degree of polymerization DP of the polyvinyl alcohol is 1000-2400,72mol%≤alcoholysis degree DH < 99.9mol%, the increasing Modeling agent be made of the glycerine of mass ratio 2-5:0-3:1-4, polyethylene glycol, two tricaprylate of triethylene glycol, the processing aid by Talcum powder, silica, oleamide, the saturated aliphatic dicarboxylic acids ester composition of mass ratio 1-3:2-5:0-2:1-6.
2. a kind of polyvinyl alcohol film, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: the poly- second Tensile strength>=20MPa of enol film, polyvinyl alcohol film oxygen transmission rate<；The melt-processable polyvinyl alcohol Resin is made of 50-85 parts of carboxy-modified polyvinyl alcohols, 5-40 parts of plasticizer, 5-35 parts of soft water and 0.1-15 parts of processing aids, It is in parts by weight；The carboxy-modified polyvinyl alcohol is after being copolymerized by vinyl acetate monomer with the unsaturated monomer containing carboxyl It is obtained through alcoholysis, alcoholysis degree 80.0-99.9mol%, the degree of polymerization are 1000~3500, and carboxyl-content is 0.1~20mol%； The plasticizer is made of the glycerine of mass ratio 1-2:0-4:3-5, polyethylene glycol, two tricaprylate of triethylene glycol, the processing Auxiliary agent is made of the talcum powder of mass ratio 0-2:0-3:2-4:1-3, silica, oleamide, saturated aliphatic dicarboxylic acids ester.
3. polyvinyl alcohol film as claimed in claim 2, the unsaturated monomer containing carboxyl is itaconic acid, acrylic acid, suitable Butene dioic acid, butyl acrylate, itaconic anhydride or/and maleic anhydride.
4. polyvinyl alcohol film as claimed in claim 1 or 2, the saturated aliphatic dicarboxylic acids ester is G32, G36 or G60.
5. a kind of polyvinyl alcohol film, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: the poly- second Tensile strength>=20MPa of enol film, polyvinyl alcohol film oxygen transmission rate<, the melt-processable polyvinyl alcohol tree Rouge is with 50-85 parts of common polythene alcohol, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids and 0.1-5 parts of crosslinkings Agent is made for raw material, is in parts by weight；The degree of polymerization DP of the polyvinyl alcohol is 1000-2400,72mol%≤alcoholysis degree DH < 99.9mol%, the plasticizer is by the glycerine of mass ratio 2-5:0-3:1-4, polyethylene glycol, two tricaprylate group of triethylene glycol At the processing aid is by the talcum powder of mass ratio 1-3:2-5:0-2:1-6, silica, oleamide, representative examples of saturated aliphatic two Carboxylate composition, the crosslinking agent is by the calcium acetate of mass ratio 0-1:1-2:0-2:0-3:3-4:1-2, zinc acetate, copper chloride, chlorine Change zinc, boric acid and borax composition.
6. a kind of polyvinyl alcohol film, using by melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: the poly- second Tensile strength>=20MPa of enol film, polyvinyl alcohol film oxygen transmission rate<；The melt-processable polyvinyl alcohol Resin is with 50-85 parts of carboxy-modified polyvinyl alcohols, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids and 0.1-5 Part crosslinking agent is made for raw material, is in parts by weight；The carboxy-modified polyvinyl alcohol is by vinyl acetate monomer and to contain carboxylic It is obtained after the unsaturated monomer copolymerization of base through alcoholysis, alcoholysis degree 80.0-99.9mol%, the degree of polymerization are 1000~3500, carboxylic Base content is 0.1~20mol%；The plasticizer is different by the glycerine of mass ratio 1-2:0-4:3-5, polyethylene glycol, triethylene glycol two Caprylate composition, the processing aid is by the talcum powder of mass ratio 0-2:0-3:2-4:1-3, silica, oleamide, saturation Aliphatic dicarboxylic acid ester composition, the crosslinking agent by the calcium acetate of mass ratio 0-3:0-2:0-4:0-5:3-5:2-4, zinc acetate, Copper chloride, zinc chloride, boric acid and borax composition.
7. polyvinyl alcohol film as claimed in claim 1 or 2, the melt-processable polyvinyl alcohol resin is graininess, cylinder Figure, circular cone figure, square figure, cuboid-type, sheet, S shape, V-arrangement, hollow circuit cylinder figure, the hollow cone bodily form, it is hollow just At least any shape in cube type, hollow cuboid-type.
8. polyvinyl alcohol film as claimed in claim 1 or 2, the melt-processable polyvinyl alcohol resin diameter is 0.5- 15mm, the cylindrical body of high 0.5-15mm.
9. polyvinyl alcohol film as described in claim 1, which is characterized in that the degree of polymerization DP of the polyvinyl alcohol is 1000- 2400,72mol%≤alcoholysis degree DH < 90mol%.
10. polyvinyl alcohol film as claimed in claim 2, the carboxy-modified polyvinyl alcohol is used by vinyl acetate monomer and clothing It is obtained after the copolymerization of health acid monomers through alcoholysis, alcoholysis degree 80.0-90.0mol%, the degree of polymerization be 1000~3500, carboxyl-content For 0.1~20mol%.
11. polyvinyl alcohol film as described in claim 1, the degree of polymerization DH of the polyvinyl alcohol be 1000-2400,90mol%≤ Alcoholysis degree DH < 95mol%.
12. polyvinyl alcohol film as claimed in claim 2, the carboxy-modified polyvinyl alcohol is used by vinyl acetate monomer and clothing It is obtained after the copolymerization of health acid monomers through alcoholysis, 90.0mol% < alcoholysis degree < 95mol%, the degree of polymerization are that 1000~3500, carboxyl contains Amount is 0.1~20mol%.
13. polyvinyl alcohol film as described in claim 1, the degree of polymerization DP of the polyvinyl alcohol is 1000-2400,95.0mol% ≤ alcoholysis degree DH < 99.9mol%.
14. polyvinyl alcohol film as claimed in claim 2, the carboxy-modified polyvinyl alcohol is used by vinyl acetate monomer and clothing It is obtained after the copolymerization of health acid monomers through alcoholysis, alcoholysis degree is 95.0-99.9 mol%, the degree of polymerization is 1000~3500, carboxyl-content For 0.1~20mol%.
15. the system of the polyvinyl alcohol film of Blown Film as described in claim 1,2,3,5,6,9,10,11,12,13 or 14 are any Preparation Method, comprising the following steps:
(1) by 50-85 parts of polymer, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, added with random order Add, be uniformly mixed under stirring and be warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, is melted under normal pressure or pressurized conditions Melt extrusion, be cooled to 20-40 DEG C, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding；
(3) resin described in (2) step is heated to molten condition, melting temperature is 130~190 DEG C, is blow molded into through Screw Extrusion Film carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.
16. the preparation method of the polyvinyl alcohol film of Blown Film as claimed in claim 4, comprising the following steps:
(1) by 50-85 parts of polymer, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, added with random order Add, be uniformly mixed under stirring and be warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, is melted under normal pressure or pressurized conditions Melt extrusion, be cooled to 20-40 DEG C, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding；
(3) resin described in (2) step is heated to molten condition, melting temperature is 130~190 DEG C, is blow molded into through Screw Extrusion Film carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.
17. the preparation method of the polyvinyl alcohol film of Blown Film as claimed in claim 7, comprising the following steps:
(1) by 50-85 parts of polymer, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, added with random order Add, be uniformly mixed under stirring and be warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, is melted under normal pressure or pressurized conditions Melt extrusion, be cooled to 20-40 DEG C, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding；
(3) resin described in (2) step is heated to molten condition, melting temperature is 130~190 DEG C, is blow molded into through Screw Extrusion Film carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.
18. the preparation method of the polyvinyl alcohol film of Blown Film as claimed in claim 8, comprising the following steps:
(1) by 50-85 parts of polymer, 5-40 parts of plasticizer, 5-35 parts of soft water, 0.1-15 parts of processing aids, added with random order Add, be uniformly mixed under stirring and be warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-200 DEG C of temperature, is melted under normal pressure or pressurized conditions Melt extrusion, be cooled to 20-40 DEG C, melt-processable polyvinyl alcohol resin is made through pelleter pelletizing moulding；
(3) resin described in (2) step is heated to molten condition, melting temperature is 130~190 DEG C, is blow molded into through Screw Extrusion Film carries out thermoplastic processing and water-soluble polyvinyl alcohol film is made.
19. the preparation method of the polyvinyl alcohol film of Blown Film as claimed in claim 15, the blending constituent of described (1) step In also add 0.1-5 parts of crosslinking agents be uniformly mixed.
20. the preparation method of the polyvinyl alcohol film of Blown Film, described (1) step as described in claim any one of 16-18 Blending constituent in also add 0.1-5 parts of crosslinking agents be uniformly mixed.
21. the preparation method of the polyvinyl alcohol film of Blown Film as claimed in claim 15, the melting extrusion Blown Film are Inflation film manufacturing machine is squeezed out using single screw rod, draw ratio is 22~28, and screw host heating zone is at least Three-section type heating melting temperature and is 130~190 DEG C, die gap is less than 1.0mm, 10~20rpm of screw speed.
22. the preparation method of the polyvinyl alcohol film of Blown Film, the melting extrusion are blown as described in claim any one of 16-18 Being moulded into film is that inflation film manufacturing machine is squeezed out using single screw rod, and draw ratio is 22~28, and it is molten that screw host heating zone is at least Three-section type heating Melting temperature is 130~190 DEG C, and die gap is less than 1.0mm, 10~20rpm of screw speed.
23. the preparation method of polyvinyl alcohol film as claimed in claim 15, it is characterised in that: hybrid mode in the step (1) Using being stirred mode；Screw extruder uses single screw extrusion machine in the step (2).
24. the preparation method of polyvinyl alcohol film as described in claim any one of 16-18, it is characterised in that: in the step (1) Hybrid mode uses and is stirred mode；Screw extruder uses single screw extrusion machine in the step (2).
25. the preparation method of melt-processable polyvinyl alcohol resin as claimed in claim 23, it is characterised in that: the step (2) screw extruder includes feeding part and screw rod melting extrusion part in, and wherein the feeding bin of feeding part is used to have and be stirred Mix the feeding bin of device.
26. the preparation method of melt-processable polyvinyl alcohol resin as claimed in claim 24, it is characterised in that: the step (2) screw extruder includes feeding part and screw rod melting extrusion part in, and wherein the feeding bin of feeding part is used to have and be stirred Mix the feeding bin of device.
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