CN106189010A - 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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CN106189010A
CN106189010A CN201510233821.4A CN201510233821A CN106189010A CN 106189010 A CN106189010 A CN 106189010A CN 201510233821 A CN201510233821 A CN 201510233821A CN 106189010 A CN106189010 A CN 106189010A
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polyvinyl alcohol
melt
mol
film
plasticizer
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CN106189010B (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 invention provides a kind of polyvinyl alcohol film, use melt-processable polyvinyl alcohol resin Blown Film, it is characterized in that: the hot strength >=20MPa of described polyvinyl alcohol film, described melt-processable polyvinyl alcohol resin includes the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, the degree of polymerization (DP) of described polyvinyl alcohol is 1000-3500, 72 (mol) %≤alcoholysis degree (DH) ＜ 99.9 (mol) %, described plasticizer is glycerol, Polyethylene Glycol, at least one in 2,2'-ethylenedioxybis(ethanol). two tricaprylate, described processing aid is Pulvis Talci, silicon dioxide, oleamide, at least one in saturated aliphatic dicarboxylic acids ester.Present invention process is simple, and equipment investment is few, and floor space is few, can be blow molded room temperature, middle temperature, the water-soluble thin film of high temperature.Mainly prepare bilayer film, be directly prepared into various water-soluble sack, for low and middle-end packaging applications field.As done pesticide, chemical products inner packing lining bag, hospital's washing packaging bag, refuse bag etc..

Description

A kind of polyvinyl alcohol film of blow molding and preparation method thereof
Technical field
The present invention relates to the polyvinyl alcohol film of a kind of blow molding, be specifically related to the poly-of low and middle-end packaging applications field Vinyl alcohol film.
Background technology
PVA film preparation method has solution casting method and melt extrudes blowing, is called wet method and dry method. Solution casting method technological process is longer, and product quality is wayward, and membrane rate is low, and energy consumption is high, and equipment investment is big, Prepared PVA film weatherability is the best, when winter, humidity was low, and the easy embrittlement of thin film, Texturized；Summer is wet When spending bigger, films tacky, size is unstable.
Melt extruding film forming is by PVA and some processing aid mixing granulations, then carries out melt extruding film forming Dry process film technique.This technique is simple, and membrane rate is high, and energy consumption is low, and floor space is little, institute's made membrane weatherability Good, dimensionally stable.
Owing to polyvinyl alcohol is polyhydroxy structure, there is intermolecular and intramolecular strong hydrogen bonding active force so that melted Temperature and decomposition temperature very close to, it is difficult to carry out thermoplastic processing.Thus, the PVA film that market is sold is basic All use the casting films that solution casting method technique is made.
Summary of the invention
It is an object of the invention to provide a kind of high-quality polyvinyl alcohol film using blow molding process to prepare.
It is an object of the invention to be realized by following measures:
A kind of polyvinyl alcohol film, uses melt-processable polyvinyl alcohol resin Blown Film, it is characterised in that: Hot strength >=the 20MPa of described polyvinyl alcohol film, described melt-processable polyvinyl alcohol resin is by effective dose Polyvinyl alcohol, plasticizer, soft water and processing aid composition, the degree of polymerization (DP) of described polyvinyl alcohol is 1000-3500,72 (mol) %≤alcoholysis degree (DH) ＜ 99.9 (mol) %, described plasticizer is glycerol, gathers At least one in ethylene glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate, described processing aid be Pulvis Talci, silicon dioxide, At least one in oleamide, saturated aliphatic dicarboxylic acids ester.
Above-mentioned polyvinyl alcohol is common polythene alcohol or carboxy-modified polyvinyl alcohol.
Above-mentioned polyvinyl alcohol film, uses common polythene alcohol as raw material, polyvinyl alcohol film oxygen transmission rate ＜ 20cm3/(m2* 24h*0.1MPa), the degree of polymerization (DP) of described polyvinyl alcohol is 1000-2400,72 (mol) %≤ Alcoholysis degree (DH) ＜ 99.9 (mol) %, described processing aid is Pulvis Talci, silicon dioxide, oleamide, satisfies With at least one in aliphatic dicarboxylic acid ester.
Above-mentioned polyvinyl alcohol film, uses carboxy-modified polyvinyl alcohol as raw material, polyvinyl alcohol film oxygen transmission rate ＜ 30cm3/(m2* 24h*0.1MPa), described carboxy-modified polyvinyl alcohol is by VAM and containing carboxyl Unsaturated monomer copolymerization after through alcoholysis obtain, its alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20mol%；Described processing aid be Pulvis Talci, silicon dioxide, At least one in oleamide, saturated aliphatic dicarboxylic acids ester.The carboxy-modified polyvinyl alcohol of the present invention contains The unsaturated monomer of carboxyl refer to the unsaturated carboxylic acid containing more than one COOH group, esters of unsaturated carboxylic acids or Unsaturated acid anhydride, such as itaconic acid, acrylic acid, maleic acid, butyl acrylate, itaconic anhydride, Malaysia Anhydride etc..
Above-mentioned saturated aliphatic dicarboxylic acids ester is by containing 2-30 C atom, the fatty acid of 1-5 COOH group With containing 1-10 C atom, the fatty acid of 1-5 OH group, this saturated aliphatic dicarboxylic acids Ester series material is commercially available prod, such as Hangzhou Jin Cheng auxiliary agent company limited produce the trade mark be G32, G36, The saturated aliphatic dicarboxylic acids ester of G60 etc..Above-mentioned glycerol, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate, Pulvis Talci, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester are known, commercially available prod.
Plasticizer of the present invention effectively reduces the melt processing temperature of PVA；On the one hand soft water of the present invention play plasticizer Effect, on the other hand play swelling action, allow PVA molecule preferably absorb plasticizer and processing aid.This Bright processing aid is good with the PVA compatibility.Above-mentioned melt-processable polyvinyl alcohol resin melt temperature is effectively dropped Low, can be used for melting thermoplastic machine-shaping, decomposition temperature is also improved, significantly improve melt-processable gathers Vinyl alcohol resin quality；Meanwhile, whole melt-processable polyvinyl alcohol resin system lubricity is good, and placement is difficult to The moisture absorption, adhesion.
In order to improve the melt-processable of melt-processable polyvinyl alcohol resin of the present invention further, improve its product Matter, it is preferable that above-mentioned resin is by the above-mentioned polyvinyl alcohol of 50-85 part, plasticizer that 5-40 part is above-mentioned, 5-35 Part above-mentioned soft water and the above-mentioned processing aid composition of 0.1-15 part.
Carry to further improve the decomposition temperature of the carboxy-modified polyvinyl alcohol resin of obtained thermoplasticity Its quality high, improves its weatherability simultaneously, and above-mentioned melt-processable polyvinyl alcohol resin is the poly-second with effective dose Enol, plasticizer, soft water, processing aid and cross-linking agent are that raw material prepares, and described cross-linking agent is calcium acetate, second At least one in acid zinc, copper chloride, zinc chloride, boric acid, Borax.
In order to preferably improve the quality of melt-processable polyvinyl alcohol resin, it is highly preferred that above-mentioned resin with Polyvinyl alcohol that 50-85 part is above-mentioned, the plasticizer that 5-40 part is above-mentioned, soft water that 5-35 part is above-mentioned, 0.1-15 The above-mentioned processing aid of part and above-mentioned 0.1-5 part cross-linking agent are that raw material prepares.
Above-mentioned melt-processable polyvinyl alcohol resin can be any shape, such as graininess, cylindrical, circle Cone-shaped, square build, cuboid-type, lamellar, disc-shaped, S shape, V-arrangement, hollow circuit cylinder build, in At least any shape in empty cone shape, hollow square build, hollow cuboid-type.
The preferred a diameter of 0.5-15mm of above-mentioned melt-processable polyvinyl alcohol resin, the cylinder of high 0.5-15mm.
Melt-processable polyvinyl alcohol resin of the present invention is by being blow molded mode by melt-processable polyvinyl alcohol Resin-made is for film forming, mainly for the preparation of bilayer film, is directly prepared into various water-soluble sack, for low and middle-end bag Dress application.As done pesticide, chemical products inner packing lining bag, hospital's washing packaging bag, refuse bag etc.. Specifically:
The preparation method of the polyvinyl alcohol film of above-mentioned Blown Film, comprises the following steps:
(1) by 50-85 part polymer, 5-40 part plasticizer, 5-35 part soft water, 0.1-15 part is processed Auxiliary agent, adds with random order, and mix homogeneously be warming up to 30-90 DEG C under stirring keeps 1/6-10 Hour；Or by 50-85 part polymer, 5-40 part plasticizer, 5-35 part soft water, 0.1-15 part is processed Auxiliary agent, 0.1-5 part cross-linking agent add with random order, mix homogeneously being warming up under stirring 30-90 DEG C, keep 1/6-10 hour；
(2) step (1) described material is delivered in screw extruder, 120-200 DEG C of temperature, often Melt extrude under pressure or pressurized conditions, be cooled to 20-40 DEG C, prepare melt-processable through pelleter pelletizing moulding Polyvinyl alcohol resin.
(3) resin described in (2nd) step being heated to molten condition, melt temperature is 130～190 DEG C, warp Screw Extrusion Blown Film, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.
Time in blending constituent described in above-mentioned (1st) step containing cross-linking agent, it is also added with 0.1-5 part cross-linking agent and mixes Close uniformly.
In above-mentioned (1st) step, the hybrid mode of material preferably employs alr mode mixing.
The preferred single screw extrusion machine of screw extruder in above-mentioned (2nd) step.
In above-mentioned (2nd) step, screw extruder is divided into feeding part and screw rod to melt extrude part, wherein feeds The feeding bin of material part uses the feeding bin with agitator.
Above-mentioned melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, screw rod The main frame thermal treatment zone is at least Three-section type heating, and melt temperature is 130～190 DEG C, and die gap is less than 1.0mm, Screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The present invention can get the molten polyvinyl alcohol film of the water-soluble polyvinyl alcohol film of high temperature, middle warm water, normal-temperature water respectively Molten polyvinyl alcohol film.
Preparing the polyvinyl alcohol film that room temperature is water-soluble, melt-processable polyvinyl alcohol resin is by the poly-second of the routine of effective dose Enol, plasticizer, soft water and processing aid composition, wherein the degree of polymerization (DP) of polyvinyl alcohol be 1000-2400, 72 (mol) %≤alcoholysis degree (DH) ＜ 90 (mol) %.Preferably, described plasticizer is mass ratio 2-5: 0-3: The glycerol of 1-4, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate form, and described processing aid is mass ratio 1-3: The Pulvis Talci of 2-5: 0-2: 1-6, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.For Preferably improving the quality of thermoplastic polyvinyl alcohol resin, raw material includes cross-linking agent.Or, melting adds Work polyvinyl alcohol resin is made up of carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, Described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, its Alcoholysis degree is 80.0-90.0 (mol) %, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20mol%； Above-mentioned plasticizer is the glycerol of mass ratio 1-2: 0-4: 3-5, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate group Becoming, described processing aid is the Pulvis Talci of mass ratio 0-2: 0-3: 2-4: 1-3, silicon dioxide, oleic acid acyl Amine, saturated aliphatic dicarboxylic acids ester form.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, former Material includes cross-linking agent, and above-mentioned cross-linking agent is preferably as 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.
The polyvinyl alcohol film that in preparation, warm water is molten: its melt-processable polyvinyl alcohol resin is gathered by the routine of effective dose Vinyl alcohol, plasticizer, soft water and processing aid composition, the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400,90 (mol) %≤alcoholysis degree (DH) ＜ 95 (mol) %.Preferably, described plasticizer is quality Than 0-1: the glycerol of 4-4.5: 2-3, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, described processing helps Agent is the Pulvis Talci of mass ratio 1-3: 0-1: 2.5-3.5: 2-4, silicon dioxide, oleamide, saturated fat Fat race dicarboxylic ester composition.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, raw material includes handing over Connection agent, cross-linking agent is preferably the calcium acetate of mass ratio 0-1: 1-2: 0-2: 0-3: 3-4: 1-2, zinc acetate, chlorination Copper, zinc chloride, boric acid and Borax composition.Or, melt-processable polyvinyl alcohol resin is by the carboxyl of effective dose Modified polyvinylalcohol, plasticizer, soft water and processing aid composition, described carboxy-modified polyvinyl alcohol uses by vinegar Obtain through alcoholysis after acid vinyl monomer and itaconic acid monomer copolymerization, its 90.0 (mol) % ＜ alcoholysis degree ＜ 95 (mol) %, the degree of polymerization are 1000～3500, carboxyl-content is 0.1～20mol%；Above-mentioned plasticizer is matter Amount is than 2-3: the glycerol of 3-4: 4-6, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, described processing helps Agent is the Pulvis Talci of mass ratio 4-5: 0-6: 3-5: 2-4, silicon dioxide, oleamide, representative examples of saturated aliphatic Dicarboxylic ester forms.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, raw material includes cross-linking agent, Described cross-linking agent is the calcium acetate of mass ratio 3-5: 1-2: 0-3: 1-2: 4-6: 5-7, zinc acetate, chlorination Copper, zinc chloride, boric acid and Borax composition.
Preparing the polyvinyl alcohol film that high temperature is water-soluble, melt-processable polyvinyl alcohol resin is by the polyethylene of effective dose Alcohol, plasticizer, soft water and processing aid composition, the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400, alcoholysis degree (DH) are 95 (mol) %-99.9 (mol) %.Preferably, described plasticizer is matter Amount is than 0-2: the glycerol of 5-6: 1-2, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, described processing helps Agent is the Pulvis Talci of mass ratio 4-5: 0-3: 4-6: 0-3, silicon dioxide, oleamide, representative examples of saturated aliphatic Dicarboxylic ester forms.In order to preferably improve the quality of thermoplastic polyvinyl alcohol resin, raw material includes cross-linking agent, Cross-linking agent is preferably the calcium acetate of mass ratio 2-3: 0-0.5: 3-4: 0-1: 1-2: 3-4, zinc acetate, chlorine Change copper, zinc chloride, boric acid and Borax composition.Or melt-processable polyvinyl alcohol resin is by the carboxyl of effective dose Modified polyvinylalcohol, plasticizer, soft water and processing aid composition, described carboxy-modified polyvinyl alcohol uses by vinegar Obtaining through alcoholysis after acid vinyl monomer and itaconic acid monomer copolymerization, its alcoholysis degree is 95.0-99.9mol%, gathers Right be 1000～3500, carboxyl-content be 0.1～20mol%；Above-mentioned plasticizer is mass ratio 0-4: 2-3: The glycerol of 4-6, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate form, and described processing aid is mass ratio 1-2: The Pulvis Talci of 1-2: 0-4: 1-3, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.For Preferably improving the quality of thermoplastic polyvinyl alcohol resin, raw material includes that cross-linking agent, described cross-linking agent are matter Amount is than 0-1: the calcium acetate of 2-3: 1-2: 0-3: 1-3: 2-4, zinc acetate, copper chloride, zinc chloride, boron Acid and Borax form.
Beneficial effect
1. present invention process is simple, and equipment investment is few, and floor space is few, can be blow molded room temperature, middle temperature, high temperature water-soluble Thin film.Mainly prepare bilayer film, be directly prepared into various water-soluble sack, for low and middle-end packaging applications field. As done pesticide, chemical products inner packing lining bag, hospital's washing packaging bag, refuse bag etc..
2. the polyvinyl alcohol film hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed) of the present invention, Film thickness >=30 μm, oxygen transmission rate ＜ 30cm3/(m2* 24h*0.1MPa), light transmittance >=70%, have water-disintegrable And biodegradable, " white pollution " will not be produced in the environment.
3. the present invention by the method for physical blending achieve PVA thermoplastic process, and be prepared for room temperature water-soluble, A series of melt-processable polyvinyl alcohol resin products that middle warm water is molten, high temperature is water-soluble, high temperature water-soluble polyvinyl alcohol The melt temperature of resin is reduced to 120-200 DEG C, dissolves in the water of 80-90 DEG C, and melt index is 2-8g/10min (160 DEG C/2.16～10kg)；Normal-temperature water contains intermingle with vinyl alcohol resin melt temperature and is reduced to 120-180 DEG C, melt index is 2-8g/10min (140 DEG C/2.16～10kg), conventional polyvinyl alcohol resin water Solubility temperature is 15-40 DEG C, carboxy-modified polyvinyl alcohol resin water solution temperature 5-30 DEG C；Middle temperature water-soluble polyvinyl alcohol Resin melt temperature is reduced to 120-200 DEG C, dissolves in the water of 40-60 DEG C, and melt index is 2-8g/10min (150 DEG C/2.16～10kg).High-temperature water contains intermingle with the PVA film water solution temperature that vinyl alcohol resin prepares 80-100 DEG C, decomposition temperature brings up to 300 DEG C-350 DEG C；The PVA that room temperature water-soluble conventional polyvinyl alcohol resin-made obtains Film water solubility temperature is 15-30 DEG C, decomposition temperature brings up to 260 DEG C-350 DEG C, carboxy-modified polyvinyl alcohol film water Solubility temperature is 5-30 DEG C, and decomposition temperature brings up to 300 DEG C-350 DEG C；Middle warm water contains intermingle with what vinyl alcohol resin prepared PVA film water solution temperature is 40-60 DEG C, and decomposition temperature brings up to 300 DEG C-350 DEG C.
4. the processing of the melt-processable polyvinyl alcohol resin product appearance water white transparency, non-yellowing of the present invention, and thermoplastic During produce without poisonous and harmful substance, processing fluidity is excellent, good moldability；Mechanics for following process Excellent performance.Film strength prepared by the present invention is high, and after drying, intensity reaches 45-120MPa；Resin lubrication is good, Nonhygroscopic, adhesion, places 1 year outward appearance, color simultaneously and also will not change；Non-toxic of the present invention, can be Degrade under conditions of Yi Ding, be conducive to environmental conservation.Adjustment thermoplastic processing technique can be prepared different field and need The water-soluble thin film of PVA asked.
The method of testing that the present invention relates to is as follows:
1. melt temperature and the test of decomposition temperature: use heat to analyze (DSC) curve and characterize, in nitrogen atmosphere Test, heating rate: 10 DEG C/min, Range of measuring temp: room temperature-250 DEG C.
2. the test of melt index: according to the thermoplastic polyvinyl alcohol resin flow behavior of the different PVA trades mark, adopt With fusion index instrument, under uniform temperature, constant pressure, measure plastic melt in 10min, flow through standard capillary The mass value of pipe, unit g/10min.This method of testing design temperature: 140 DEG C～180 DEG C；Pressure: 2.16kg～ 10kg。
3. thin film stretching strength determination: with reference to standard GB/T 13022-91 stretched plastic film performance test side Method is tested.
4. thin film oxygen transmission rate test: with reference to GB GB/T1038-2000 plastic sheeting and the examination of thin slice gas-premeable Proved recipe method pressure differential method.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that, the present embodiment is only It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention, this field The present invention is made some nonessential improvement and adjustment according to foregoing by person skilled in the art, still falls within this Bright protection domain.In the following example, unless otherwise, all % and number are all to contain with percent mass Amount, mass weight are unit.
Embodiment 1: by 50 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 72.0 (mol) %), 40 parts of poly-second two Alcohol, 20 parts of soft water, 0.1 part of oleamide mix homogeneously under stirring, stir below 30 DEG C of temperature Limit is heated, and stops heating after 10 minutes.Then being added by material in the feed bin with stirring, employing screw rod will Material automatic transport, in screw extruder, keeps extruder temperature 120 DEG C, melt extrudes in atmospheric conditions, Again material is cooled to 20 DEG C, prepares thermoplastic polyvinyl alcohol resin through pelleter pelletizing moulding.By gained heat Plastic polyethylene alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into Normal-temperature water contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, major diameter Ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 130～190 DEG C, mould Mouth gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained thermoplastic polyvinyl alcohol resin is 260 DEG C, resin water white transparency, non-yellowing, molten Melting temperature 140 DEG C, melt index 5g/10min (140 DEG C/2.16～10kg), resin is graininess, water dissolution Temperature is 20-30 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 31 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, 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 glycerol, 18 parts of soft water, 0.5 part of silicon dioxide mixing, mix homogeneously under stirring, stirs below 40 DEG C of temperature Mix limit heating, after 30 minutes, stop heating.Then material is added in the feed bin with stirring, use screw rod By in material automatic transport to single screw extrusion machine, keep extruder temperature 130 DEG C, in 0.01MPa (gauge pressure) Melt extrude under pressure condition, then material is cooled to 30 DEG C, prepare thermoplastic poly through pelleter pelletizing moulding Vinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the side of Screw Extrusion blowing Formula, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with alcohol film.Described melt extrude Blown Film be use single Screw Extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melted Temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed according to Extruded velocity regulates.
The decomposition temperature of gained resin is 265 DEG C, melt temperature 130 DEG C, melt index 4g/10min (140 DEG C/2.16～10kg), resin is diameter 2.0mm, the cylinder of high 0.5mm, water dissolution Temperature is 15-30 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 36 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)
Embodiment 3: by 40 parts of conventional polyvinyl alcohol (degree of polymerization 1500, alcoholysis degree 88.0 (mol) %), 32 part three Glycol two tricaprylate, 17 parts of soft water, 1 part of Pulvis Talci mixing, mix homogeneously under stirring, at 50 DEG C At a temperature of heat while stirring, after 60 minutes stop heating.Then material is added in the feed bin with stirring, Use single screw rod by material automatic transport to single screw extrusion machine, keep extruder temperature 130 DEG C, at normal pressure bar Melt extrude under part, then material is cooled to 35 DEG C, prepare thermoplastic polyvinyl alcohol through pelleter pelletizing moulding Resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, enters Row thermoplastic is processed into normal-temperature water and is contained intermingle with alcohol film.It is described that to melt extrude Blown Film be to use single screw rod to squeeze Going out inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed is according to extrusion speed Degree regulation.
The decomposition temperature of gained resin is 270 DEG C, melt temperature 145 DEG C, melt index 5g/10min (140 DEG C/2.16～10kg), resin is square shape, and water solubility temperature is 20-35 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 32 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)
Embodiment 4: by 65 parts of conventional polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 86.0 (mol) %), 28 parts of matter Measuring the glycerol that ratio is 1: 1 is the dioxy of 2: 1 with Polyethylene Glycol mixture, 35 parts of soft water, 2 parts of mass ratioes SiClx mixes with the blend of oleamide, by material mix homogeneously, 60 DEG C of temperature heating 2 hours, so Rear stopping is heated.Then material is added in single screw extrusion machine, keep extruder temperature 130 DEG C, at normal pressure bar Melt extrude under part, then material is cooled to 35 DEG C, prepare thermoplastic polyvinyl alcohol through pelleter pelletizing moulding Resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, enters Row thermoplastic is processed into normal-temperature water and is contained intermingle with alcohol film.It is described that to melt extrude Blown Film be to use single screw rod to squeeze Going out inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 130～190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed is according to extrusion speed Degree regulation.
The decomposition temperature of gained resin is 272 DEG C, melt temperature 150 DEG C, 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 the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 39 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 5: by 50 parts of conventional polyvinyl alcohol (degree of polymerization 1200, alcoholysis degree 78.0 (mol) %), 25 part three Glycol two tricaprylate, 10 parts of soft water, 5 parts of oleamide mixing, mix homogeneously under stirring, Heat while stirring at a temperature of 60 DEG C, after 3 hours, stop heating.Then material is added the feed bin with stirring In, use twin screw by material automatic transport to single screw extrusion machine, keep extruder temperature 140 DEG C, Melt extrude under 0.05MPa pressure condition, then material is cooled to 40 DEG C, prepare heat through pelleter pelletizing moulding Plastic polyethylene alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, blows through Screw Extrusion The mode moulded, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with alcohol film.Described melt extrude Blown Film and be Using Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, Melt temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed Regulate according to extruded velocity.
The decomposition temperature of gained resin is 280 DEG C, melt temperature 160 DEG C, melt index 6g/10min (140 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 3mm height 3mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 37 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)
Embodiment 6: by 75 parts of polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 80.0 (mol) %), 17 parts of mass ratioes Be 3.5: 1.5: 2.5 glycerol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate and the mixture of Polyethylene Glycol, 8 parts of soft water, 10 parts of mass ratioes are that the Pulvis Talci of 2: 3.5 mixes with the mixture of silicon dioxide, and under stirring, mixing is all Even, heat while stirring at a temperature of 90 DEG C, after 4 hours, stop heating.Then material is added with stirring Feed bin in, use twin screw by material automatic transport to single screw extrusion machine, keep extruder temperature 150 DEG C, Melt extrude in atmospheric conditions, then material is cooled to 30 DEG C, prepare thermoplasticity through pelleter pelletizing moulding Polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through Screw Extrusion blowing Mode, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, molten Melting temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed root Regulate according to extruded velocity.
The decomposition temperature of gained resin is 275 DEG C, melt temperature 170 DEG C, melt index 7g/10min (140 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 4mm height 6mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 33 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 7: by 80 parts of conventional polyvinyl alcohol (degree of polymerization 1800, alcoholysis degree 85.0 (mol) %), 10 part third Triol, 5 parts of soft water, 15 parts of saturated aliphatic dicarboxylic acids ester G32 mixing, mix homogeneously under stirring, Heat while stirring at a temperature of 80 DEG C, after 5 hours, stop heating.Then material is added the material with stirring In storehouse, use screw rod by material automatic transport to single screw extrusion machine, keep extruder temperature 160 DEG C, often Melt extrude under the conditions of pressure, then material is cooled to 25 DEG C, prepare thermoplastic poly second through pelleter pelletizing moulding Enol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, Carry out thermoplastic to be processed into normal-temperature water and contain intermingle with alcohol film.It is described that to melt extrude Blown Film be to use single screw rod Extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melt temperature Being 150～190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed is according to extrusion Speed regulates.
The decomposition temperature of gained resin is 270 DEG C, melt temperature 130 DEG C, melt index 8g/10min (140 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 2mm height 15mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 31 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 8: by 85 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 82.0 (mol) %), 5 parts of mass ratioes Be 5: 4 glycerol and 2,2'-ethylenedioxybis(ethanol). two tricaprylate, 14 parts of soft water, 6 parts of mass ratioes be the cunning of 3: 5: 1 Stone powder, silicon dioxide and saturated aliphatic dicarboxylic acids ester G36,2 parts of cross-linking agent calcium acetate mixing, at stirring shape Mix homogeneously under state, heats at a temperature of 90 DEG C while stirring, stops heating after 6 hours.Then material is added Enter in the feed bin with stirring, use twin screw by material automatic transport to single screw extrusion machine, keep screw rod Temperature 180 DEG C, melt extrudes in atmospheric conditions, then material is cooled to 30 DEG C, through pelleter pelletizing moulding Prepare thermoplastic polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through screw rod The mode of extrusion-blown modling, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with alcohol film.Described melt extrude blowing Film forming is to use Single screw extrusion inflation film manufacturing machine, and draw ratio is 22～28, and the screw host thermal treatment zone is at least three sections Formula heats, and melt temperature is 130～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm. Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 290 DEG C, melt temperature 180 DEG C, melt index 5g/10min (140 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 10mm height 5mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 260-350 DEG C, and water solution temperature is 15-30 DEG C, thickness 34 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 9: (this carboxy-modified polyvinyl alcohol is by VAM by 85 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after the monomer copolymerization of itaconic acid, its alcoholysis degree is 80 (mol) %, the degree of polymerization is 3500, carboxyl Content is 20mol%), 20 parts of Polyethylene Glycol, 20 parts of glycerol, 20 parts of soft water, 15 parts of satisfied fatty acid Race dicarboxylic ester G60 mix homogeneously under stirring, heats while stirring at a temperature of 30 DEG C, stops after 10h Only heating.Then material is added in the feed bin with stirring, use screw rod material automatic transport to be squeezed to screw rod Go out in machine, keep extruder temperature 200 DEG C, melt extrude in atmospheric conditions, then material is cooled to 40 DEG C, The carboxy-modified polyvinyl alcohol resin of thermoplasticity is prepared through pelleter pelletizing moulding.By gained thermoplastic polyvinyl alcohol tree Fat is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with ethylene Alcohol thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, The screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 320 DEG C, resin water white transparency, no Jaundice, melt temperature 125 DEG C, melt index 5.5g/10min (140 DEG C/2.16～10kg), resin is granule Shape, water solubility temperature is 5-20 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 5-30 DEG C, thickness 33 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 10: (this carboxy-modified polyvinyl alcohol is by VAM by 52 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after itaconic anhydride copolymerization, its alcoholysis degree is 90 (mol) %, the degree of polymerization is 1000, and carboxyl contains Amount is for 9mol%), 5 parts of glycerol, 7 parts of soft water, 0.1 part of silicon dioxide, 0.1 part of oleamides mixing, Mix homogeneously under stirring, heats at a temperature of 90 DEG C while stirring, stops heating after 10 minutes.Connect And material added in the feed bin with stirring, use screw rod by material automatic transport to single screw extrusion machine, Keep extruder temperature 120 DEG C, melt extrude under 0.01MPa (gauge pressure) pressure condition, then material is cooled down To 20 DEG C, prepare the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding.By gained thermoplasticity Polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into room temperature Water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die orifice stitches Gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 300 DEG C, melt temperature 140 DEG C, Melt index 2.5g/10min (140 DEG C/2.16～10kg), resin is diameter 2.0mm, the cylinder of high 0.5mm Body, water solubility temperature is 5-15 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 5-30 DEG C, thickness 35 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 11: (this carboxy-modified polyvinyl alcohol is by VAM by 65 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after acrylic acid copolymer, its alcoholysis degree is 85 (mol) %, the degree of polymerization is 2000, carboxyl-content For 0.1mol%), 28 parts of 2,2'-ethylenedioxybis(ethanol). two tricaprylates, 13 parts of soft water, 5 parts of Pulvis Talci, 5 parts of saturated fats Acid race dicarboxylic ester G36 mixing, mix homogeneously under stirring, heat while stirring at a temperature of 60 DEG C, Heating is stopped after 2h.Then material is added in the feed bin with stirring, use single screw rod that material is the most defeated Deliver in single screw extrusion machine, keep extruder temperature 150 DEG C, melt extrude in atmospheric conditions, then by material It is cooled to 30 DEG C, prepares the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding.By gained heat Plastic polyethylene alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into Normal-temperature water contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, major diameter Ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, mould Mouth gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 350 DEG C, melt temperature 170 DEG C, Melt index 4g/10min (140 DEG C/2.16～10kg), square shape, water solubility temperature is 20-30 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 5-30 DEG C, thickness 37 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 12: (this carboxy-modified polyvinyl alcohol is by VAM by 85 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after butyl acrylate copolymerization, its alcoholysis degree is 88 (mol) %, the degree of polymerization is 2500, carboxyl Content is 3mol%), 30 parts of mass ratioes be 1: 4 glycerol and 2,2'-ethylenedioxybis(ethanol). two tricaprylate, 8 parts of soft water, 12 parts of mass ratioes are Pulvis Talci, silicon dioxide and the saturated aliphatic dicarboxylic acids ester G32 of 2: 3: 1,5 parts of matter The zinc chloride of amount ratio 4: 1 and boric acid mix homogeneously under stirring, heat at a temperature of 80 DEG C while stirring, Heating is stopped after 1 hour.Then material is added in the feed bin with stirring, use twin screw that material is automatic It is delivered in single screw extrusion machine, keeps extruder temperature 140 DEG C, melt extrude in atmospheric conditions, then by thing Material is cooled to 30 DEG C, prepares the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding.By gained Thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic processing system Normal-temperature water is become to contain intermingle with alcohol film.Described to melt extrude Blown Film be to use Single screw extrusion inflation film manufacturing machine, long Footpath ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, Die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 330 DEG C, melt temperature 130 DEG C, Melt index 6g/10min (140 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 10mm height 5mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 5-30 DEG C, thickness 32 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 13: by 80 parts of polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 90.0 (mol) %), 36 part three sweet Alcohol two tricaprylate, 20 parts of soft water, 2.5 parts of oleamides, 2 parts of mix homogeneously under stirring of Pulvis Talci, Heat while stirring at a temperature of 60 DEG C, after 5h, stop heating.Then material is added the feed bin with stirring In, use screw rod by material automatic transport to screw extruder, keep extruder temperature 160 DEG C, at normal pressure bar Melt extrude under part, then material is cooled to 30 DEG C, prepare graininess melting through pelleter pelletizing moulding and add Work polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, is blow molded through Screw Extrusion Mode, carry out thermoplastic and be processed into water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use single Screw Extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melted Temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed according to Extruded velocity regulates.
The decomposition temperature of gained resin is 300 DEG C, water white transparency, non-yellowing, melt temperature 150 DEG C, melted Index 6.5g/10min (150 DEG C/2.16～10kg), resin is graininess, and water solubility temperature is 45-55 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 32 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, 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 poly-second two Alcohol, 5 parts of soft water, 0.1 part of silicon dioxide mixing, mix homogeneously under stirring, following 30 DEG C of temperature The heating of stirring limit, stops heating after 9h.Then being added by material in the feed bin with stirring, employing screw rod will Material automatic transport, in single screw extrusion machine, keeps screw rod temperature 200 DEG C, at 0.01MPa (gauge pressure) pressure Under the conditions of melt extrude, then material is cooled to 40 DEG C, prepares melt-processable through pelleter pelletizing moulding and gather Vinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the side of Screw Extrusion blowing Formula, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.It is described that to melt extrude Blown Film be to use single screw rod Extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melt temperature Being 150～190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed is according to extrusion Speed regulates.
The decomposition temperature of gained resin is 260 DEG C, melt temperature 130 DEG C, melt index 4g/10min (150 DEG C/2.16～10kg), resin is diameter 2.0mm, the cylinder of high 0.5mm, water dissolution Temperature is 42-47 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 40 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 15: by 85 parts of conventional polyvinyl alcohol (degree of polymerization 2200, alcoholysis degree 93.0 (mol) %), 40 parts Glycerol, 30 parts of soft water, 15 parts of saturated aliphatic dicarboxylic acids ester G36 mix homogeneously, heat 90 DEG C of temperature 10 minutes, then stop heating.Then material is added in single screw extrusion machine, keeps extruder temperature 120 DEG C, Melt extrude in atmospheric conditions, then material is cooled to 20 DEG C, prepare melting through pelleter pelletizing moulding Processing polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, blows through Screw Extrusion The mode moulded, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, molten Melting temperature is 150～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed root Regulate according to extruded velocity.
The decomposition temperature of gained resin is 310 DEG C, melt temperature 130 DEG C, 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 the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 35 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 16: by 65 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 92.0 (mol) %), 25 parts of quality Than be 1: 2 glycerol and 2,2'-ethylenedioxybis(ethanol). two tricaprylate, 15 parts of soft water, 10 parts of mass ratioes be the two of 1: 3 Silicon oxide and oleamide, 3 parts of cross-linking agent Borax mixing, mix homogeneously under stirring, 80 DEG C of temperature Under heat while stirring, after 2 hours stop heating.Then material is added in the feed bin with stirring, use Twin screw, by material automatic transport to single screw extrusion machine, keeps extruder temperature 150 DEG C, in atmospheric conditions Melt extrude, then material is cooled to 35 DEG C, prepare melt-processable polyvinyl alcohol through pelleter pelletizing moulding Resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, enters Row thermoplastic is processed into water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use Single screw extrusion blow Film machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melt temperature be 150～ 190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 290 DEG C, melt temperature 170 DEG C, melt index 5g/10min (150 DEG C/2.16～10kg), the cylindrical shape of diameter 15mm height 15mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 38 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 17: (this carboxy-modified polyvinyl alcohol is by VAM by 70 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after the monomer copolymerization of itaconic acid, its alcoholysis degree is 92 (mol) %, the degree of polymerization is 2200, carboxyl Content is 12mol%), 28 parts of 2,2'-ethylenedioxybis(ethanol). two tricaprylates, 2 parts of glycerol, 15 parts of soft water, 5 parts saturated Fatty acid group dicarboxylic ester G32,2 parts of oleamide mix homogeneously under stirring, following 44 DEG C of temperature The heating of stirring limit, stops heating after 3h.Then being added by material in the feed bin with stirring, employing screw rod will Material automatic transport, in screw extruder, keeps extruder temperature 135 DEG C, melt extrudes in atmospheric conditions, Again material is cooled to 25 DEG C, prepares the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding. Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic It is processed into middle warm water and contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion blown film Machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melt temperature be 150～ 190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 340 DEG C, water white transparency, non-yellowing, Melt temperature 125 DEG C, melt index 6.5g/10min (150 DEG C/2.16～10kg), resin is graininess, water Solution temperature is 52-60 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 36 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 18: (this carboxy-modified polyvinyl alcohol is by VAM by 80 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after itaconic anhydride copolymerization, its alcoholysis degree is 94 (mol) %, the degree of polymerization is 3500, and carboxyl contains Amount is for 17mol%), 10 parts of glycerol, 16 parts of Polyethylene Glycol, 18 parts of soft water, 5 parts of silicon dioxide, 9 parts Oleamide mixes, and mix homogeneously under stirring heats, 30 minutes at a temperature of 90 DEG C while stirring Rear stopping is heated.Then material is added in the feed bin with stirring, use screw rod by material automatic transport to list In screw extruder, keep extruder temperature 200 DEG C, melt extrude under 0.01MPa (gauge pressure) pressure condition, Again material is cooled to 40 DEG C, prepares the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding. Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic It is processed into middle warm water and contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion blown film Machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melt temperature be 150～ 190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 305 DEG C, melt temperature 156 DEG C, Melt index 3.5g/10min (150 DEG C/2.16～10kg), water solubility temperature is 40-48 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 34 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 19: (this carboxy-modified polyvinyl alcohol is by VAM by 55 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after butyl acrylate copolymerization, its alcoholysis degree is 93 (mol) %, the degree of polymerization is 2800, carboxyl Content is 0.5mol%), 7 parts of 2,2'-ethylenedioxybis(ethanol). two tricaprylates, 8 parts of soft water, 0.8 part of silicon dioxide, 0.2 part Oleamide mixes, and mix homogeneously under stirring heats while stirring at a temperature of 35 DEG C, stops after 6h Only heating.Then material is added in the feed bin with stirring, use single screw rod by material automatic transport to single spiral shell In bar extruder, keep extruder temperature 180 DEG C, melt extrude in atmospheric conditions, then material is cooled to 20 DEG C, prepare the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding.By gained thermoplastic poly second Enol resin is heated to molten condition, and through the mode of Screw Extrusion blowing, carrying out thermoplastic, to be processed into room temperature water-soluble Polyvinyl alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio be 22～ 28, the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is little In 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 320 DEG C, melt temperature 160 DEG C, Melt index 5g/10min (150 DEG C/2.16～10kg), resin is square shape, and water solubility temperature is 45-55℃。
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 30 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 20: (this carboxy-modified polyvinyl alcohol is by VAM by 63 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after acrylic acid copolymer, its alcoholysis degree is 91 (mol) %, the degree of polymerization is 1500, carboxyl-content For 6mol%), 22 parts of mass ratioes be 1: 1 glycerol and Polyethylene Glycol, 11 parts of soft water, 5 parts of mass ratioes Be Pulvis Talci, silicon dioxide and the oleamide of 2: 3: 5,5 parts of mass ratioes be 3: 1: 4 calcium acetate, Zinc chloride and boric acid mixing, mix homogeneously under stirring, heat, 2.6 at a temperature of 60 DEG C while stirring Heating is stopped after hour.Then material is added in the feed bin with stirring, use twin screw that material is the most defeated Deliver in single screw extrusion machine, keep extruder temperature 160 DEG C, melt extrude in atmospheric conditions, then by material It is cooled to 40 DEG C, prepares the carboxy-modified polyvinyl alcohol resin of thermoplasticity through pelleter pelletizing moulding.By gained heat Plastic polyethylene alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into Middle warm water contains intermingle with alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, major diameter Ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, mould Mouth gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of the carboxy-modified polyvinyl alcohol resin of gained thermoplasticity is 310 DEG C, melt temperature 160 DEG C, Melt index 7g/10min (150 DEG C/2.16～10kg).
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 40-60 DEG C, thickness 36 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 21: by 50 parts of polyvinyl alcohol (degree of polymerization 2000, alcoholysis degree 95.0 (mol) %), 6 parts of 2,2'-ethylenedioxybis(ethanol) .s Two tricaprylates, 5 parts of soft water, 0.1 part of saturated aliphatic dicarboxylic acids ester G32 mix homogeneously under stirring, Heat while stirring at a temperature of 90 DEG C, after 7h, stop heating.Then material is added the feed bin with stirring In, use screw rod by material automatic transport to screw extruder, keep extruder temperature 200 DEG C, at normal pressure bar Melt extrude under part, then material is cooled to 40 DEG C, prepare graininess melting through pelleter pelletizing moulding and add Work polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, is blow molded through Screw Extrusion Mode, carry out thermoplastic and be processed into water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use single Screw Extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, melted Temperature is 130～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed according to Extruded velocity regulates.
The decomposition temperature of gained resin is 320 DEG C, water white transparency, non-yellowing, melt temperature 180 DEG C, melted Index 5g/10min (160 DEG C/2.16～10kg), resin is graininess, and water solubility temperature is 60-68 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-100 DEG C, thickness 36 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, 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 poly-second Glycol, 20 parts of glycerol, 20 parts of soft water, 10 parts of silicon dioxide, 5 parts of oleamide mixing, at stirring shape Mix homogeneously under state, heats at a temperature of 30 DEG C while stirring, stops heating after 10h.Then material is added In feed bin with stirring, use screw rod by material automatic transport to single screw extrusion machine, keep screw rod temperature 120 DEG C, melt extrude under 0.01MPa (gauge pressure) pressure condition, then material is cooled to 20 DEG C, through cutting Grain machine pelletizing moulding prepares melt-processable polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to Molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.Described Melt extruding Blown Film is to use Single screw extrusion inflation film manufacturing machine, and draw ratio is 22～28, and screw host heats District is at least Three-section type heating, and melt temperature is 130～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 350 DEG C, melt temperature 120 DEG C, melt index 4g/10min (160 DEG C/2.16～10kg), resin is diameter 2.0mm, the cylinder of high 0.5mm, water dissolution Temperature is 90-100 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-100 DEG C, thickness 35 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 23: by 70 parts of conventional polyvinyl alcohol (degree of polymerization 1000, alcoholysis degree 99.9 (mol) %), 30 parts Polyethylene Glycol, 16 parts of soft water, 7 parts of saturated aliphatic dicarboxylic acids ester G36,3 parts of silicon dioxide mix homogeneously, Heat 2h 55 DEG C of temperature, then stop heating.Then material is added in single screw extrusion machine, keep spiral shell Bar temperature 145 DEG C, melt extrudes in atmospheric conditions, then material is cooled to 25 DEG C, makes through pelleter pelletizing Type prepares melt-processable polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, Through the mode of Screw Extrusion blowing, carry out thermoplastic and be processed into water-soluble polyvinyl alcohol thin film.Described melt extrude blow Being moulded film is to use Single screw extrusion inflation film manufacturing machine, and draw ratio is 22～28, and the screw host thermal treatment zone is at least three Segmentation heats, and melt temperature is 130～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm. Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 260 DEG C, melt temperature 165 DEG C, 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 the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-100 DEG C, thickness 32 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 24: by 60 parts of polyvinyl alcohol (degree of polymerization 1500, alcoholysis degree 96.0 (mol) %), 30 parts of quality Than be 5: 1 Polyethylene Glycol and 2,2'-ethylenedioxybis(ethanol). two tricaprylate, 13 parts of soft water, 7 parts of mass ratioes be the cunning of 1: 1 Stone powder and oleamide, the boric acid of 1.5 parts of mass ratioes 1: 2 and copper chloride mix homogeneously under stirring, Heat while stirring at a temperature of 68 DEG C, after 4.5 hours, stop heating.Then material is added with stirring In feed bin, use twin screw by material automatic transport to single screw extrusion machine, keep extruder temperature 136 DEG C, Melt extrude in atmospheric conditions, then material is cooled to 25 DEG C, prepare melting through pelleter pelletizing moulding Processing polyvinyl alcohol resin.Gained thermoplastic polyvinyl alcohol resin is heated to molten condition, blows through Screw Extrusion The mode moulded, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, and the screw host thermal treatment zone is at least Three-section type heating, molten Melting temperature is 130～190 DEG C, and die gap is less than 1.0mm, screw speed 10～20rpm.Hauling speed root Regulate according to extruded velocity.
The decomposition temperature of gained resin is 315 DEG C, melt temperature 150 DEG C, melt index 6.5g/10min (160 DEG C/2.16～10kg), resin is the cylindrical shape of diameter 2mm height 3mm.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-100 DEG C, thickness 33 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 20cm3/(m2*24h*0.1MPa)。
Embodiment 25: (this carboxy-modified polyvinyl alcohol is by VAM by 60 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after the monomer copolymerization of itaconic acid, its alcoholysis degree is 95mol%, the degree of polymerization is 1600, carboxyl contains Amount is for 10mol%), 8 parts of Polyethylene Glycol, 2 parts of 2,2'-ethylenedioxybis(ethanol). two tricaprylates, 9 parts of soft water, 2 parts of oleic acid acyls Amine is mix homogeneously under stirring, heats while stirring at a temperature of 90 DEG C, stops heating after 10min.Connect And material is added in the feed bin with stirring, use screw rod by material automatic transport to screw extruder, protect Hold extruder temperature 200 DEG C, melt extrude in atmospheric conditions, then material is cooled to 40 DEG C, cut through pelleter Grain moulding prepares the carboxy-modified high-temperature water of thermoplasticity and contains intermingle with vinyl alcohol resin.By gained thermoplastic polyvinyl alcohol resin It is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and be processed into room temperature water-soluble polyvinyl alcohol Thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, spiral shell The bar main frame thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is less than 1.0mm, Screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 300 DEG C, water white transparency, non-yellowing, melt temperature 130 DEG C, melted Index 3g/10min (160 DEG C/2.16～10kg), resin is graininess, and water solubility temperature is 80-85 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-90 DEG C, thickness 35 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 26: (this carboxy-modified polyvinyl alcohol is by VAM by 70 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after itaconic anhydride copolymerization, its alcoholysis degree is 99mol%, the degree of polymerization is 2000, carboxyl-content For 12mol%), 18 parts of Polyethylene Glycol, 15 parts of soft water, 8 parts of oleamides mixing, mixed under stirring Close uniformly, heat while stirring at a temperature of 30 DEG C, after 6 minutes, stop heating.Then by material add with In the feed bin of stirring, use screw rod by material automatic transport to single screw extrusion machine, keep extruder temperature 120 DEG C, melt extrude under 0.01MPa (gauge pressure) pressure condition, then material is cooled to 20 DEG C, through cutting Grain machine pelletizing moulding prepares the carboxy-modified high-temperature water of thermoplasticity and contains intermingle with vinyl alcohol resin.By gained thermoplastic polyethylene Alcohol resin is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and is processed into normal-temperature water and contains intermingle with Alcohol film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio be 22～ 28, the screw host thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is little In 1.0mm, screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 310 DEG C, melt temperature 140 DEG C, melt index 5g/10min (160 DEG C/2.16～10kg), water solubility temperature is 85-88 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-90 DEG C, thickness 38 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 27: (this carboxy-modified polyvinyl alcohol is by VAM by 85 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after acrylic acid copolymer, its alcoholysis degree is 98mol%, the degree of polymerization is 3500, and carboxyl-content is 2mol%), 40 parts of 2,2'-ethylenedioxybis(ethanol). two tricaprylates, 20 parts of soft water, 13 parts of silicon dioxide, 2 parts of oleamides, Mix homogeneously under stirring, heats at a temperature of 50 DEG C while stirring, stops heating after 3h.Then will Material adds in the feed bin with stirring, uses single screw rod by material automatic transport to single screw extrusion machine, protects Hold extruder temperature 170 DEG C, melt extrude in atmospheric conditions, then material is cooled to 30 DEG C, cut through pelleter Grain moulding prepares the carboxy-modified high-temperature water of thermoplasticity and contains intermingle with vinyl alcohol resin.By gained thermoplastic polyvinyl alcohol resin It is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and be processed into high temperature water-soluble polyvinyl alcohol Thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, spiral shell The bar main frame thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is less than 1.0mm, Screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 350 DEG C, melt temperature 180 DEG C, melt index 6g/10min (160 DEG C/2.16～10kg), water solubility temperature is 85-90 DEG C.
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-90 DEG C, thickness 35 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。
Embodiment 28: (this carboxy-modified polyvinyl alcohol is by VAM by 65 parts of carboxy-modified polyvinyl alcohol Obtaining through alcoholysis with after butyl acrylate copolymerization, its alcoholysis degree is 99.9mol%, the degree of polymerization is 1200, carboxyl Content is 20mol%), 5 parts of glycerol, 16 parts of soft water, 10 parts of mass ratioes be 1: 1: 3 Pulvis Talci, Silicon dioxide and saturated aliphatic dicarboxylic acids ester G36, the boric acid of 3 parts of mass ratioes 1: 2 and zinc acetate mixing, Mix homogeneously under stirring, heats at a temperature of 80 DEG C while stirring, stops heating after 1 hour.Then will Material adds in the feed bin with stirring, uses twin screw by material automatic transport to single screw extrusion machine, protects Hold extruder temperature 140 DEG C, melt extrude in atmospheric conditions, then material is cooled to 40 DEG C, cut through pelleter Grain moulding prepares the carboxy-modified high-temperature water of thermoplasticity and contains intermingle with vinyl alcohol resin.By gained thermoplastic polyvinyl alcohol resin It is heated to molten condition, through the mode of Screw Extrusion blowing, carries out thermoplastic and be processed into high temperature water-soluble polyvinyl alcohol Thin film.Described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, spiral shell The bar main frame thermal treatment zone is at least Three-section type heating, and melt temperature is 150～190 DEG C, and die gap is less than 1.0mm, Screw speed 10～20rpm.Hauling speed regulates according to extruded velocity.
The decomposition temperature of gained resin is 330 DEG C, melt temperature 125 DEG C, melt index 6g/10min (160 DEG C/2.16～10kg).
The decomposition temperature of the polyvinyl alcohol film of gained is 300-350 DEG C, and water solution temperature is 80-90 DEG C, thickness 32 μm, hot strength >=20MPa (23 DEG C, 50%RH, 100mm/min draw speed), elongation at break 100%-300%, light transmittance more than 70.0%, oxygen transmission rate ＜ 30cm3/(m2*24h*0.1MPa)。

Claims (33)

1. a polyvinyl alcohol film, use melt-processable polyvinyl alcohol resin Blown Film, it is characterized in that: the hot strength >=20MPa of described polyvinyl alcohol film, described melt-processable polyvinyl alcohol resin includes the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, the degree of polymerization (DP) of described polyvinyl alcohol is 1000-3500, 72 (mol) %≤alcoholysis degree (DH) ＜ 99.9 (mol) %, described plasticizer is glycerol, Polyethylene Glycol, at least one in 2,2'-ethylenedioxybis(ethanol). two tricaprylate, described processing aid is Pulvis Talci, silicon dioxide, oleamide, at least one in saturated aliphatic dicarboxylic acids ester.
2. polyvinyl alcohol film as claimed in claim 1, uses common polythene alcohol as raw material, polyvinyl alcohol film oxygen transmission rate < 20cm3/(m2* 24h*0.1MPa), the degree of polymerization (DP) of described polyvinyl alcohol is 1000-2400,72 (mol) %≤alcoholysis degree (DH) ＜ 99.9 (mol) %.
3. polyvinyl alcohol film as claimed in claim 1, uses carboxy-modified polyvinyl alcohol as raw material, polyvinyl alcohol film oxygen transmission rate < 30cm3/(m2* 24h*0.1MPa), described carboxy-modified polyvinyl alcohol is to be obtained through alcoholysis after the unsaturated monomer copolymerization containing carboxyl by VAM, its alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is 1000～3500, and carboxyl-content is 0.1～20 mol%。
4. polyvinyl alcohol film as claimed in claim 3, the described unsaturated monomer containing carboxyl is that itaconic acid, acrylic acid, maleic acid, butyl acrylate, itaconic anhydride are or/and maleic anhydride.
5. the polyvinyl alcohol film as described in claim 1,2 or 3, described saturated aliphatic dicarboxylic acids ester is G32, G36 or G60.
6. the polyvinyl alcohol film as described in claim 1,2 or 3, described melt-processable polyvinyl alcohol resin is made up of the soft water described in the polyvinyl alcohol described in 50-85 part, the plasticizer described in 5-40 part, 5-35 part and the processing aid described in 0.1-15 part.
7. the polyvinyl alcohol film as described in claim 1,2 or 3, described melt-processable polyvinyl alcohol resin is to prepare with polyvinyl alcohol, plasticizer, soft water, processing aid and the cross-linking agent of effective dose for raw material, and described cross-linking agent is at least one in calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, Borax.
8. polyvinyl alcohol film as claimed in claim 7, described melt-processable polyvinyl alcohol resin prepares with the processing aid described in the plasticizer described in the polyvinyl alcohol described in 50-85 part, 5-40 part, the soft water described in 5-35 part, 0.1-15 part and described 0.1-5 part cross-linking agent for raw material.
9. the polyvinyl alcohol film as described in claim 1,2 or 3, described melt-processable polyvinyl alcohol resin is at least any shape in graininess, cylindrical, cone shape, square build, cuboid-type, lamellar, disc-shaped, S shape, V-arrangement, hollow circuit cylinder build, the hollow cone bodily form, hollow square build, hollow cuboid-type.
10. the polyvinyl alcohol film as described in claim 1,2 or 3, the described a diameter of 0.5-15mm of melt-processable polyvinyl alcohol resin, the cylinder of high 0.5-15mm.
11. polyvinyl alcohol films as claimed in claim 2, described melt-processable polyvinyl alcohol resin includes the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, wherein the degree of polymerization (DP) of polyvinyl alcohol be 1000-2400,72 (mol) %≤alcoholysis degree (DH) ＜ 90 (mol) %.
12. polyvinyl alcohol films as claimed in claim 11, described melt-processable polyvinyl alcohol resin is made up of common polythene alcohol, plasticizer, soft water and the processing aid of effective dose, described plasticizer is the glycerol of mass ratio 2-5:0-3:1-4, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 1-3:2-5:0-2:1-6, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
13. polyvinyl alcohol films as claimed in claim 11, described melt-processable polyvinyl alcohol resin raw material includes cross-linking agent, and cross-linking agent uses boric acid.
14. polyvinyl alcohol films as claimed in claim 3, described melt-processable polyvinyl alcohol resin includes carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its alcoholysis degree is 80.0-90.0 (mol) %, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20 mol%。
15. polyvinyl alcohol films as claimed in claim 14, described melt-processable polyvinyl alcohol resin is made up of carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its alcoholysis degree is 80.0-90.0 (mol) %, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20 mol%；Described plasticizer is the glycerol of mass ratio 1-2:0-4:3-5, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 0-2:0-3:2-4:1-3, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
16. polyvinyl alcohol films as claimed in claim 14, described melt-processable polyvinyl alcohol resin raw material includes that cross-linking agent, described cross-linking agent are 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.
17. polyvinyl alcohol films as claimed in claim 2, described melt-processable polyvinyl alcohol resin includes the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, and the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400,90 (mol) %≤alcoholysis degree (DH) ＜ 95 (mol) %.
18. polyvinyl alcohol films as claimed in claim 17, described melt-processable polyvinyl alcohol resin is made up of the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, and the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400,90 (mol) %≤alcoholysis degree (DH) ＜ 95 (mol) %；Described plasticizer is the glycerol of mass ratio 0-1:4-4.5:2-3, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 1-3:0-1:2.5-3.5:2-4, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
19. polyvinyl alcohol films as claimed in claim 17, described melt-processable polyvinyl alcohol resin raw material includes cross-linking agent, and cross-linking agent is the calcium acetate of mass ratio 0-1:1-2:0-2:0-3:3-4:1-2, zinc acetate, copper chloride, zinc chloride, boric acid and Borax composition.
20. polyvinyl alcohol films as claimed in claim 3, described melt-processable polyvinyl alcohol resin is made up of carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its 90.0 (mol) % ＜ alcoholysis degree ＜ 95 (mol) %, the degree of polymerization are 1000～3500, carboxyl-content is 0.1～20 mol%.
21. polyvinyl alcohol films as claimed in claim 20, described melt-processable polyvinyl alcohol resin is made up of carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its 90.0 (mol) % ＜ alcoholysis degree ＜ 95 (mol) %, the degree of polymerization are 1000～3500, carboxyl-content is 0.1～20 mol%；Described plasticizer is the glycerol of mass ratio 2-3:3-4:4-6, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 4-5:0-6:3-5:2-4, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
22. polyvinyl alcohol films as claimed in claim 20, polyvinyl alcohol film as claimed in claim 20, raw material includes that cross-linking agent, described cross-linking agent are the calcium acetate of mass ratio 3-5:1-2:0-3:1-2:4-6:5-7, zinc acetate, copper chloride, zinc chloride, boric acid and Borax composition.
23. polyvinyl alcohol films as claimed in claim 2, described melt-processable polyvinyl alcohol resin includes the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, and the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400, alcoholysis degree (DH) is 95 (mol) %-99.9 (mol) %.
24. polyvinyl alcohol films as claimed in claim 23, described melt-processable polyvinyl alcohol resin is made up of the polyvinyl alcohol of effective dose, plasticizer, soft water and processing aid, and the degree of polymerization (DP) of wherein said polyvinyl alcohol is 1000-2400, alcoholysis degree (DH) is 95 (mol) %-99.9 (mol) %；Described plasticizer is the glycerol of mass ratio 0-2:5-6:1-2, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 4-5:0-3:4-6:0-3, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
25. polyvinyl alcohol films as claimed in claim 23, described melt-processable polyvinyl alcohol resin raw material includes cross-linking agent, and cross-linking agent is the calcium acetate of mass ratio 2-3:0-0.5:3-4:0-1:1-2:3-4, zinc acetate, copper chloride, zinc chloride, boric acid and Borax composition.
26. polyvinyl alcohol films as claimed in claim 3, described melt-processable polyvinyl alcohol resin includes carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its alcoholysis degree is 95.0-99.9 mol%, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20 mol%。
27. polyvinyl alcohol films as claimed in claim 26, described melt-processable polyvinyl alcohol resin is made up of carboxy-modified polyvinyl alcohol, plasticizer, soft water and the processing aid of effective dose, described carboxy-modified polyvinyl alcohol uses and is obtained through alcoholysis after the monomer copolymerization of itaconic acid by VAM, and its alcoholysis degree is 95.0-99.9 mol%, the degree of polymerization is 1000～3500, carboxyl-content is 0.1～20 mol%；Described plasticizer is the glycerol of mass ratio 0-4:2-3:4-6, Polyethylene Glycol, 2,2'-ethylenedioxybis(ethanol). two tricaprylate composition, and described processing aid is the Pulvis Talci of mass ratio 1-2:1-2:0-4:1-3, silicon dioxide, oleamide, saturated aliphatic dicarboxylic acids ester composition.
28. polyvinyl alcohol films as claimed in claim 27, described melt-processable polyvinyl alcohol resin raw material includes that cross-linking agent, described cross-linking agent are the calcium acetate of mass ratio 0-1:2-3:1-2:0-3:1-3:2-4, zinc acetate, copper chloride, zinc chloride, boric acid and Borax composition.
29. as described in claim 1-28 is arbitrary the preparation method of the polyvinyl alcohol film of Blown Film, comprise the following steps:
(1) by 50-85 part polymer, 5-40 part plasticizer, 5-35 part soft water, 0.1-15 part processing aid, add with random order, mix homogeneously be warming up to 30-90 DEG C under stirring, keep 1/6-10 hour；
(2) step (1) described material is delivered in screw extruder, melt extrudes under 120-200 DEG C of temperature, normal pressure or pressurized conditions, be cooled to 20-40 DEG C, prepare melt-processable polyvinyl alcohol resin through pelleter pelletizing moulding；
(3) resin described in (2nd) step being heated to molten condition, melt temperature is 130～190 DEG C, through Screw Extrusion Blown Film, carries out thermoplastic and is processed into water-soluble polyvinyl alcohol thin film.
The preparation method of the polyvinyl alcohol film of 30. Blown Films as claimed in claim 29, is also added with 0.1-5 part cross-linking agent mix homogeneously in the blending constituent of described (1st) step.
The preparation method of the polyvinyl alcohol film of 31. Blown Films as claimed in claim 29, described melt extrude Blown Film be use Single screw extrusion inflation film manufacturing machine, draw ratio is 22～28, the screw host thermal treatment zone at least Three-section type heating melt temperature is 130～190 DEG C, die gap is less than 1.0mm, screw speed 10～20rpm.
The preparation method of 32. polyvinyl alcohol films as claimed in claim 29, it is characterised in that: in described step (1), hybrid mode uses stirring hybrid mode；In described step (2), screw extruder uses single screw extrusion machine.
The preparation method of 33. melt-processable polyvinyl alcohol resins as claimed in claim 32, it is characterized in that: in described step (2), screw extruder includes that feeding part and screw rod melt extrude part, wherein the feeding bin of feeding part uses the feeding bin with agitator.
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CN109181183B (en) * 2018-08-24 2021-05-18 中山市新领航塑化科技有限公司 Preparation method of water-resistant PVA biodegradable film
CN110294910A (en) * 2019-07-08 2019-10-01 秦皇岛祥祺新材料科技有限公司 A kind of high temperature water-soluble polyvinyl alcohol master batch and preparation method thereof
CN110294910B (en) * 2019-07-08 2022-04-15 秦皇岛祥祺新材料科技有限公司 High-temperature water-soluble polyvinyl alcohol master batch and preparation method thereof
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CN115521563B (en) * 2021-06-25 2024-05-03 中国石油化工股份有限公司 Thermoplastic low-alcoholysis-degree ternary polyvinyl alcohol film with medium-temperature water solubility and preparation method and application thereof

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