CN109721905B - Polyvinyl alcohol film, composition and preparation method thereof - Google Patents
Polyvinyl alcohol film, composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of polyvinyl alcohol films, in particular to a polyvinyl alcohol film, a composition and a preparation method thereof. The polyvinyl alcohol composition contains polyvinyl alcohol, a plasticizer, modified polypropylene, a lubricant and optional auxiliary agents; the modified polypropylene is acrylate graft modified polypropylene; the plasticizer contains a component A, a component B and a component C; the component A is one or more of glycerol, glycol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, calcium chloride, copper sulfate and sodium acetate; the component C is water. The invention can make the polyvinyl alcohol with wider alcoholysis degree range into the film by biaxial stretching, and the obtained polyvinyl alcohol film has higher mechanical property, barrier property and optical property.
Description
Technical Field
The invention relates to the field of polyvinyl alcohol films, in particular to a polyvinyl alcohol film, a composition and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is a few of industrially produced non-petroleum-based polymer materials that can be prepared from natural gas, and has applications in the fields of textiles, food, medicine, construction, wood processing, paper making, printing, agriculture, steel, polymer chemical industry, and the like. PVA has excellent acid and alkali resistance and organic solvent resistance, excellent barrier performance, good biocompatibility and biodegradability. However, due to the existence of a polyhydroxy structure on a molecular chain, strong hydrogen bonds are generated in molecules and among molecules, so that the melting point and the decomposition temperature of the PVA film are close to each other, and the PVA film is difficult to be processed in a thermoplastic way.
The biaxial stretching method has the advantages of large stretching ratio (the transverse stretching ratio can reach more than 10 times), high forming speed (the highest winding speed can reach hundreds of meters per minute), high production efficiency, and better mechanical strength, optical performance and thickness uniformity of the obtained film, but the film forming is obviously influenced by the fluctuation of process conditions, the film stretching processing difficulty is large, and the biaxial stretching method has higher requirements on film raw materials. And due to the particularity of PVA processing, the research of a process system of a biaxial stretching method aiming at PVA is not provided, so that the PVA film is difficult to prepare by the biaxial stretching method.
At present, some researches on plasticization of PVA are carried out, and it is desired to improve the plasticity of PVA by means of copolymerization, blending, etc. so as to enable thermoplastic processing, thereby reducing the preparation cost and expanding the application range of PVA. At present, PVA films (such as CN106189010A, CN106189008A, CN101864132A, CN102391598A and the like) are mostly designed and prepared by adopting a melt processing method, but the films are prepared by adopting a casting method or a film blowing method, the two methods have relatively lower requirements on raw materials and processes, and the performance of the films is poorer than that of a biaxial stretching method.
CN106189006A proposes a biaxial stretching method for preparing PVA film, but said method needs to use PVA raw material whose alcoholysis degree is more than or equal to 95 (mol)% and less than 99.9 (mol)%, and has narrow applicability to PVA; and the resulting PVA film has a limited increase in tensile strength.
Disclosure of Invention
The invention aims to provide a novel polyvinyl alcohol film, a composition thereof and a preparation method thereof.
In order to achieve the above objects, one aspect of the present invention provides a polyvinyl alcohol composition comprising polyvinyl alcohol, a plasticizer, modified polypropylene, a lubricant and optionally an auxiliary; the modified polypropylene is acrylate graft modified polypropylene; the plasticizer contains a component A, a component B and a component C; the component A is one or more of glycerol, glycol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, calcium chloride, copper sulfate and sodium acetate; the component C is water.
In a second aspect, the present invention provides a polyvinyl alcohol film comprising the above composition.
The third aspect of the present invention provides a method for producing a biaxially oriented polyvinyl alcohol film, comprising:
(1) Providing a mixture of the ingredients contained in the composition;
(2) Carrying out melt extrusion on the mixture and casting the mixture into a casting sheet to obtain a polyvinyl alcohol casting sheet;
(3) The cast piece of polyvinyl alcohol was biaxially stretched to form a film.
In a fourth aspect, the present invention provides a polyvinyl alcohol film produced by the above method.
The invention can make the polyvinyl alcohol with wider alcoholysis degree range into the film by biaxial stretching, and the obtained polyvinyl alcohol film has higher mechanical property, barrier property and optical property.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a polyvinyl alcohol composition, which comprises polyvinyl alcohol, a plasticizer, modified polypropylene, a lubricant and optional auxiliary agents; the modified polypropylene is acrylic ester graft modified polypropylene; the plasticizer contains a component A, a component B and a component C; the component A is one or more of glycerol, glycol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, calcium chloride, copper sulfate and sodium acetate; the component C is water.
According to the invention, the contents of the component A, the component B and the component C can be changed in a wide range, in order to obtain the polyvinyl alcohol film which is more beneficial to improving the mechanical property, the barrier property and the optical property of the polyvinyl alcohol film and obtain the polyvinyl alcohol which can be better compounded with the modified polypropylene, the weight ratio of the component A, the component B and the component C is preferably 20-500:100:80-500, preferably 30-300:100:100-300, for example 50-200:100:120-250, 80-150:100:150-200.
According to the invention, the polyethylene glycol in component A preferably has an average molecular weight of 200 to 400. The component A is preferably one or more of glycerol, polyethylene glycol with the average molecular weight of 200-400 and pentaerythritol.
Preferably, the component B is one or more of magnesium chloride, magnesium nitrate and calcium chloride.
In a preferred embodiment of the present invention, the component a is glycerol and/or polyethylene glycol having a number average molecular weight of 200 to 400, and the component B is magnesium chloride and/or magnesium nitrate; or the component A is pentaerythritol and the component B is calcium chloride.
According to the present invention, in order to obtain a polyvinyl alcohol film having higher mechanical properties, barrier properties and optical properties, it is preferable that the weight ratio of the polyvinyl alcohol to the plasticizer is 100:5-40, preferably 100:10-30, more preferably 100:15-25. Preferably, the weight ratio of the polyvinyl alcohol to the modified polypropylene is 100:10-100, preferably 100:10-40. Preferably, the weight ratio of the polyvinyl alcohol to the lubricant is 100:0.5 to 5, preferably 100:1-3.
The composition of the invention is suitable for polyvinyl alcohol with wide range of alcoholysis degree, polymerization degree and particle size, preferably, the alcoholysis degree of the polyvinyl alcohol is 80-99mol%, the polymerization degree is more than 1500 (preferably 1500-2500), and the particle size is 90-500 μm. Also suitable are polyvinyl alcohols having a low degree of alcoholysis, for example 80 to 90mol%, a degree of polymerization of 1600 to 1800 and a particle size of 100 to 300. Mu.m. A polyvinyl alcohol having a high degree of alcoholysis, for example a polyvinyl alcohol having a degree of alcoholysis of from 95 to 99mol%, a degree of polymerization of from 1700 to 2500 and a particle size of from 320 to 400 μm, is also suitable.
According to the invention, the modified polypropylene is acrylate graft modified polypropylene, wherein the acrylate used for the modified polypropylene is preferably one or more of methyl acrylate, ethyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate and Glycidyl Methacrylate (GMA), and more preferably glycidyl methacrylate.
The modified polypropylene can be prepared by a method conventional in the art, for example, by graft copolymerizing a polypropylene powder and an acrylic acid ester in an aqueous salt solution in the presence of an initiator. Wherein, the polypropylene can be cellular homo-polypropylene and/or co-polypropylene. Preferably, the melt index of the homopolymerized polypropylene is 2.5-4g/10min, and the melt index of the copolymerized polypropylene is 5.5-8g/10min. Such polypropylene powder may be obtained by a conventional manner in the art, and may be, for example, a commercially available product such as T30S (homopolymer type) of china petrochemical zhenhai oil refinery, ltd, SP179 (copolymer type) of china petrochemical zilu petrochemical company, and the like.
The amount of the acrylic ester used may vary within wide limits and is generally from 2 to 10% by weight, based on the amount of polypropylene powder.
The salt used in the aqueous salt solution may be a soluble inorganic salt that does not participate in the graft copolymerization reaction, and may be one or more of a halogen salt of an alkali metal (for example, sodium chloride, potassium chloride, sodium bromide, potassium bromide, etc.), a carbonate of an alkali metal (for example, sodium carbonate, potassium carbonate, etc.), a hydrogen carbonate of an alkali metal (for example, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), a dihydrogen phosphate of an alkali metal (for example, sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc.), a sulfate of an alkali metal (for example, sodium sulfate, potassium sulfate, etc.), and the like, and the concentration of the salt in the aqueous salt solution may vary within a wide range, and may be, for example, 5 to 20% by weight. The amount of said aqueous salt solution may vary within wide limits and may, for example, be preferably from 100 to 500 parts by weight, relative to 100 parts by weight of polypropylene powder.
Wherein, the initiator can be selected from various types, can be one or more of thermal decomposition type initiators, is preferably one or more selected from peroxide type initiators and azobisnitrile type compound initiators, and is more preferably one or more selected from dicumyl peroxide, benzoyl peroxide, dibenzoyl peroxide, di-o-methylbenzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile and azobisisoheptonitrile. Preferably, the initiator is used in an amount of 0.1 to 1 wt% based on the amount of the acrylate.
The conditions of the graft copolymerization reaction may include, for example: the temperature is 60-80 ℃ and the time is 4-10h.
According to the present invention, the lubricant may be selected from a plurality of lubricants, and preferably, the lubricant is one or more of a polyethylene glycol lubricant, a fluoropolymer lubricant, a silicone lubricant, a fatty alcohol lubricant, a fatty acid ester lubricant, a stearic acid amide lubricant, a fatty acid metal soap lubricant, an alkane and alkane oxide lubricant, and a micro-nano particle lubricant.
The polyethylene glycol lubricant may be, for example, PEG molecules with an average molecular weight of 500 to 50000, which may be subjected to capping, grafting, crosslinking, or other chemical or physical modification.
The fluoropolymer lubricant may be at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, and the like, or may be another unimodal or multimodal fluoropolymer or a crystalline or semicrystalline fluoropolymer.
The organic silicon lubricant can be various compounds which take carbon and silicon atoms as molecular main chains and take oligomers or oligomers of organic groups such as methyl, phenyl, alkoxy, vinyl and the like as side chains.
The fatty alcohol-based lubricant may be at least one of a soft fatty alcohol, a hard fatty alcohol, a tallow fatty alcohol, and the like.
The fatty acid-based lubricant may be, for example, stearic acid and/or 12-hydroxystearic acid.
The fatty acid ester lubricant may be at least one of butyl stearate, monoglyceride stearate, cetyl palmitate, stearyl stearate, and the like.
The stearic acid amide-based lubricant may be at least one of stearic acid amide, oleic acid amide, erucic acid amide, n-ethylene bis stearic acid amide (EBS), and the like.
The fatty acid metal soap lubricant may be at least one of lead stearate, calcium stearate, magnesium stearate, synthetic calcium acetate, and the like.
The alkane and the oxidized alkane lubricant may be at least one of liquid paraffin, solid paraffin, polyethylene wax, polypropylene wax, and ethylene oxide wax, for example.
The nanoparticle lubricant may be, for example, a powder rubber and/or silica gel microparticle.
According to the invention, the composition may also contain an auxiliary agent, which may be an additive that has a gain effect on other properties of the polyvinyl alcohol film and does not adversely affect the stretch film forming properties, mechanical properties, barrier properties and optical properties of the polyvinyl alcohol film. The auxiliary agent may be, for example, one or more of an antioxidant, an acid-absorbing agent, an antistatic agent, and an antiblocking agent.
The antioxidant may be at least one of antioxidant 1010, antioxidant 1076, antioxidant 164, antioxidant 168, antioxidant 264, and the like. The content of the antioxidant may vary within a wide range, and is preferably 0.1 to 1 part by weight relative to 100 parts by weight of the polyvinyl alcohol.
The acid acceptor may be at least one of hydrotalcite, calcium stearate, zinc stearate, and the like. The content of the acid scavenger can be varied within a wide range, and is preferably 0.1 to 1 part by weight relative to 100 parts by weight of the polyvinyl alcohol.
Among them, the antistatic agent may be, for example, at least one of ethoxylated alkylamine, glyceryl monostearate, sodium alkylsulfate, and the like. The content of the antistatic agent may vary within wide limits, and is preferably 0.1 to 1 part by weight relative to 100 parts by weight of the polyvinyl alcohol.
The anti-sticking agent may be at least one of silica, calcium carbonate, diatomaceous earth, talc, glass beads, and the like. The content of the antiblocking agent can vary within wide limits, and the content of the antiblocking agent is preferably from 0.1 to 1 part by weight, based on 100 parts by weight of the polyvinyl alcohol.
In a second aspect, the present invention provides a polyvinyl alcohol film comprising the above composition.
The polyvinyl alcohol film provided by the second aspect of the present invention may contain the polyvinyl alcohol composition, and the content thereof may be, for example, 80 to 100% by weight.
The third aspect of the present invention provides a method for producing a biaxially oriented polyvinyl alcohol film, comprising:
(1) Providing a mixture of the ingredients contained in the composition;
(2) Carrying out melt extrusion on the mixture and casting the mixture into a sheet to obtain a polyvinyl alcohol casting sheet;
(3) The cast piece of polyvinyl alcohol was biaxially stretched to form a film.
According to the invention, step (1) consists essentially in providing a mixture of the constituents of the above-mentioned composition, in order to facilitate the subsequent processing to form a polyvinyl alcohol film. Preferably, step (1) comprises: the polyvinyl alcohol and the plasticizer are mixed first, and then the modified polypropylene, the lubricant and the optional auxiliary agent are introduced. More preferably, the conditions for mixing the polyvinyl alcohol and the plasticizer include: the temperature is 50-90 deg.C (preferably 60-80 deg.C), and the time is 0.5-4h (preferably 1-2 h).
The mixing process can be that the polyvinyl alcohol is heated to 50-90 ℃, then the plasticizer is introduced and mixed for 0.5-4h at the temperature of 50-90 ℃. The plasticizer can be introduced in a one-time feeding mode or a step-by-step feeding mode, in order to improve the dispersing effect of the plasticizer and the polyvinyl alcohol, the step-by-step feeding mode is preferably adopted, and the plasticizer is preferably added within 5-60 min.
According to the invention, after the polyvinyl alcohol and the plasticizer are mixed, before the modified polypropylene, the lubricant and the optional auxiliary agent are added, the mixture of the polyvinyl alcohol and the plasticizer is cooled to room temperature (for example, 20-30 ℃), then the modified polypropylene, the lubricant and the optional auxiliary agent are added, and then the mixture is fully mixed to obtain the mixture of the components contained in the composition.
According to the invention, before the step (2), the mixture obtained in the step (1) can be subjected to extrusion granulation (the temperature of the extrusion granulation is 100-200 ℃), and the obtained master batch is used for the operation of the step (2); of course, it is preferred to directly subject the mixture obtained in step (1) to the treatment of step (2) in order to reduce the material loss, in particular the loss of plasticizer.
According to the invention, the step (2) of melt extruding the mixture and casting the cast sheet can be carried out in a casting machine, preferably, the temperature of the melt extrusion is 100-200 ℃; the casting chill roll temperature of the cast sheet is 15 to 50 deg.C (preferably 20 to 40 deg.C).
According to the present invention, the casting sheet die used for the casting sheet may be selected according to the structure of the film to be obtained, for example, when a thin film having a single-layer structure is to be obtained, a single-layer die may be used; when it is desired to obtain a film having a multilayer structure (a film having a three-layer structure of an upper surface layer, a core layer and a lower surface layer), a multilayer-structure composite die may be used, and at least one layer (core layer) of the multilayer-structure composite die may be communicated with an extruder hopper containing the above-mentioned polyvinyl alcohol composition, so that at least one layer (core layer) of the obtained cast sheet is a polyvinyl alcohol layer formed from the above-mentioned polyvinyl alcohol composition, or the multilayer-structure composite die may be communicated with an extruder hopper containing the above-mentioned polyvinyl alcohol composition, so that each layer of the obtained cast sheet is a polyvinyl alcohol layer formed from the above-mentioned polyvinyl alcohol composition.
For this purpose, the cast polyvinyl alcohol sheet has a single-layer structure or a multi-layer structure, preferably a three-layer structure consisting of an upper surface layer, a core layer, and a lower surface layer, and the upper surface layer, the core layer, and the lower surface layer are all layers formed of a polyvinyl alcohol composition.
According to the present invention, in the step (3), the biaxial stretching may include simultaneous stretching or stepwise stretching. Wherein the synchronous stretching means that the longitudinal (MD) and Transverse (TD) stretching of the film are simultaneously performed, and the step-by-step stretching means that the longitudinal stretching of the film is performed first, and then the transverse stretching of the film is performed.
Preferably, the simultaneous stretching comprises preheating the cast polyvinyl alcohol sheet prior to simultaneous MD and TD stretching. Preferably, the conditions for the simultaneous stretching include: a stretching temperature of 120 to 170 ℃, a MD stretching ratio of 3 times or more (for example, 3 to 6 times), a TD stretching ratio of 3 times or more (for example, 3 to 6 times), a MD stretching rate of 300%/s or more (for example, 300%/s to 500%/s), a TD stretching rate of 300%/s or more (for example, 300%/s to 500%/s)
Preferably, the step-wise stretching comprises: the method comprises the steps of preheating a polyvinyl alcohol casting sheet, then carrying out MD stretching, then preheating and then carrying out TD stretching. Preferably, the conditions for the step-wise stretching include: the MD stretching temperature is 80 to 150 ℃, the TD stretching temperature is 120 to 200 ℃, the MD stretching ratio is 3 times or more (for example, 3 to 6 times), the TD stretching ratio is 3 times or more (for example, 3 to 6 times), the MD stretching rate is 100%/s or more (for example, 100%/s to 200%/s), and the TD stretching rate is 100%/s or more (for example, 100%/s to 200%/s).
According to the present invention, the method may or may not perform the annealing setting treatment on the stretched film, and may further include, after the step (3), annealing setting treatment of the obtained film, wherein the annealing setting treatment is preferably performed at a temperature of 180 to 200 ℃. The time for the annealing setting treatment is preferably 5 to 60 seconds. The annealing and setting treatment of the stretched film can improve the dimensional stability of the film.
According to the present invention, the method may further comprise subjecting the resulting polyvinyl alcohol film to surface corona treatment, edge slitting and winding treatment, which are conventional operations in the art, and the present invention is not particularly limited thereto.
In a fourth aspect, the present invention provides a polyvinyl alcohol film produced by the above method.
The polyvinyl alcohol film obtained by the invention has higher mechanical property, barrier property and optical property, and the MD tensile strength of the polyvinyl alcohol film can be more than 45MPa, particularly more than 60MPa, preferably more than 100MPa, and more preferably 100-200MPa; the TD tensile strength may be, for example, 55MPa or more, particularly 70MPa or more, preferably 100MPa or more, more preferably 110 to 200MPa;the light transmittance is more than 90%, and preferably 92-94%; the oxygen permeability may be, for example, 1.6cc/m 2 Day or less, preferably 1.4cc/m 2 Day or less, more preferably 0.05 to 1.4cc/m 2 Day.
For a polyvinyl alcohol film obtained from polyvinyl alcohol having a high degree of alcoholysis (for example, 95 to 99 mol%), the MD tensile strength of the polyvinyl alcohol film is 130MPa or more, preferably 150 to 200MPa; TD tensile strength is more than 150MPa, preferably 170-200MPa; the light transmittance is more than 90%, and preferably 92-94%; the oxygen permeability is 1.3cc/m 2 Less than day, preferably 0.05-1.3cc/m 2 Day.
The polyvinyl alcohol film obtained from polyvinyl alcohol having a low alcoholysis degree (for example, 80 to 90 mol%) may have an MD tensile strength of, for example, 45MPa or more, particularly 60MPa or more, preferably 100MPa or more, and more preferably 110 to 135MPa; the TD tensile strength may be, for example, 55MPa or more, particularly 70MPa or more, preferably 100MPa or more, more preferably 120 to 155MPa; the light transmittance is more than 90%, and preferably 92-94%; the oxygen permeability is 1.6cc/m 2 Less than day, preferably 0.5-1.4cc/m 2 Day.
The present invention will be described in detail below by way of examples.
In the following examples:
PEG200 is polyethylene glycol with an average molecular weight of 200 purchased from Guangdi chemical research institute.
PEG400 is polyethylene glycol with an average molecular weight of 400, which is purchased from the institute of photo-chemical engineering, tianjin.
The tensile strength, elongation at break and tensile elastic modulus of the polyvinyl alcohol film were measured according to the methods specified in GB/T1040.3-2006;
the light transmittance and haze of the polyvinyl alcohol film were measured according to the methods specified in GB/T2410-2008;
the oxygen permeability of the polyvinyl alcohol film was measured according to the method specified in astm d-3985.
Preparation example of plasticizer
According to the formula of table 1, component a, component B and component C were mixed in proportion to obtain the corresponding plasticizer.
TABLE 1
Note: the above components A and B are metered as pure substances from the substances listed in the table.
Modified Polypropylene preparation example 1
Heating 200 parts by weight of 10 wt% sodium chloride aqueous solution to 70 ℃, adding 100 parts by weight of polypropylene powder (melt index 3.0g/10min, T30s of China petrochemical and oil refining chemical Co., ltd.), 6 parts by weight of monomer GMA and 0.06 part by weight of initiator benzoyl peroxide into the sodium chloride aqueous solution, stirring and mixing, reacting for 6 hours, washing the reaction product by deionized water and acetone to remove unreacted monomer and initiator, and drying to obtain GMA modified polypropylene particles PP-1.
Modified Polypropylene preparation example 2
Heating 200 parts by weight of 10 wt% sodium chloride aqueous solution to 70 ℃, adding 100 parts by weight of polypropylene powder (melt index 3.0g/10min, T30s of China petrochemical and oil refining chemical Co., ltd.), 2 parts by weight of monomer GMA and 0.02 part by weight of initiator benzoyl peroxide into the sodium chloride aqueous solution, stirring, mixing and reacting for 5 hours, washing the reaction product by deionized water and acetone to remove unreacted monomer and initiator, and drying to obtain GMA modified polypropylene particles PP-2.
Modified Polypropylene preparation example 3
Heating 200 parts by weight of 10 wt% sodium chloride aqueous solution to 70 ℃, adding 100 parts by weight of polypropylene powder (with a melt index of 8.0g/10min, SP179 of Chile petrochemical company, china), 10 parts by weight of monomer GMA and 0.03 part by weight of initiator dicumyl peroxide into the sodium chloride aqueous solution, stirring, mixing, reacting for 7 hours, washing the reaction product with deionized water and acetone to remove unreacted monomer and initiator, and drying to obtain GMA modified polypropylene particles PP-3.
Example 1
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
(1) Heating 100 parts by weight of polyvinyl alcohol (alcoholysis degree of 88mol%, polymerization degree of 1700, particle size of 180 μm, available from Shanxi three-dimensional group Co., ltd.) to 60 deg.C, and gradually adding 15 parts by weight of plasticizer E1 dropwise (after the addition is completed within 30 min); after the addition was complete, the temperature was kept at 50 ℃ with stirring for 1h. Naturally cooling to 30 ℃, adding 1 part by weight of polyvinylidene fluoride lubricant (from FX5911 brand of 3M company), 10 parts by weight of modified polypropylene particles PP-1 and 0.25 part by weight of antioxidant 1010 (from Ciba chemical (China) Co., ltd., switzerland, the same shall apply hereinafter) into the mixture, uniformly mixing the mixture, and then granulating the mixture in a WP25 type double-screw extruder at the granulation temperature of 160-200 ℃ to obtain the polyvinyl alcohol composition;
(2) Adding the polyvinyl alcohol composition prepared in the step (1) into a core layer extruder, an upper surface layer extruder and a lower surface layer extruder of a multilayer extrusion casting machine of Labtech company, sweden, of which the model is LCR400, for melt extrusion and casting, wherein the temperature of each section of melt extrusion is 140-190 ℃, and the temperature of a casting quenching roller is 25 ℃, so as to obtain a polyvinyl alcohol casting sheet consisting of an upper surface layer, a core layer and a lower surface layer;
(3) Putting the polyvinyl alcohol casting sheet into a stretching clamp of film biaxial stretching equipment, and adopting biaxial step-by-step stretching to prepare a film, wherein the method comprises the following steps: preheating a polyvinyl alcohol casting sheet, then performing MD stretching, then preheating and then performing TD stretching; the conditions include: preheating temperature before MD stretching is 120 ℃, MD stretching temperature is 120 ℃, MD stretching multiplying power is 3 times, and the MD stretching speed of the film is 100%/s; preheating temperature before TD stretching is 140 ℃, TD stretching temperature is 140 ℃, TD stretching multiplying power is 4 times, and TD stretching speed of the film is 100%/s; then, the film obtained by biaxial stretching was subjected to annealing setting treatment at 180 ℃ for 30 seconds to obtain a film having an average thickness of 25 μm, which was composed of an upper surface layer, a core layer and a lower surface layer, each layer being made of the polyvinyl alcohol composition of the present example. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 2
This example illustrates the polyvinyl alcohol film of the invention, its composition and preparation.
(1) Heating 100 parts by weight of polyvinyl alcohol (alcoholysis degree of 85mol%, polymerization degree of 1500, particle size of 200 μm, available from Shanxi three-dimensional group Co., ltd.) to 70 deg.C, and gradually adding 20 parts by weight of plasticizer E2 dropwise (after adding the plasticizer within 25 min); after the addition was complete, the temperature was kept at 60 ℃ with stirring and mixing for 1.5h. Naturally cooling to 30 ℃, adding 2 parts by weight of polyethylene glycol lubricant (purchased from Laine corporation, switzerland, average molecular weight 10000), 20 parts by weight of modified polypropylene particles PP-2, 0.15 part by weight of antioxidant 1010 and 0.25 part by weight of antioxidant 168 (purchased from Ciba chemistry (China) Co., ltd., switzerland), and uniformly mixing to obtain the polyvinyl alcohol composition;
(2) Adding the polyvinyl alcohol composition prepared in the step (1) into a core layer extruder, an upper surface layer extruder and a lower surface layer extruder of a multilayer extrusion casting machine of Labtech company, sweden, of which the model is LCR400, for melt extrusion and casting, wherein the temperature of each section of melt extrusion is 100-170 ℃, and the temperature of a casting quenching roller is 20 ℃, so as to obtain a polyvinyl alcohol casting sheet consisting of an upper surface layer, a core layer and a lower surface layer;
(3) Putting the polyvinyl alcohol casting sheet into a stretching clamp of film biaxial stretching equipment, and adopting biaxial step-by-step stretching to prepare a film, wherein the method comprises the following steps: preheating a polyvinyl alcohol casting sheet, then performing MD stretching, then preheating and then performing TD stretching; the conditions include: preheating temperature before MD stretching is 130 ℃, MD stretching temperature is 130 ℃, MD stretching multiplying power is 5 times, and the MD stretching speed of the film is 100%/s; preheating temperature before TD stretching is 160 ℃, TD stretching temperature is 160 ℃, TD stretching multiplying power is 5 times, and TD stretching speed of the film is 150%/s; then, the film obtained by biaxial stretching was subjected to annealing setting treatment at 200 ℃ for 10 seconds to obtain a film having an average thickness of 25 μm and composed of an upper surface layer, a core layer and a lower surface layer, each layer being made of the polyvinyl alcohol composition of the present example. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 3
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The method of embodiment 1, except that:
step (1): 25 parts by weight of plasticizer E3 is used for replacing E1, 30 parts by weight of modified polypropylene particles PP-3 are used for replacing modified polypropylene particles PP-1, and 1 part by weight of glycerol monostearate (available from Atmer 163 trade mark of Dakoku company) is used as a lubricant;
and (3): preheating temperature before TD stretching is 170 ℃, and TD stretching temperature is 170 ℃;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Examples 4 to 11
This example illustrates the polyvinyl alcohol film of the invention, its composition and preparation.
According to the method described in example 1, except that equal parts by weight of the plasticizers E4 to E11 were used instead of E1, films each having an average thickness of 25 μm were finally obtained, which consisted of an upper surface layer, a core layer and a lower surface layer, each of which was made of the polyvinyl alcohol composition of this example. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 12
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The method of example 1 except that the plasticizer is used in an amount of 5 parts by weight;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 13
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The method of example 1 except that the plasticizer was used in an amount of 35 parts by weight;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 14
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The process of example 1 except that the modified polypropylene particles PP-1 were 50 parts by weight;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 15
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The process of example 1, except that the modified polypropylene particles PP-1 are 100 parts by weight;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 16
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The method of embodiment 1, except that:
step (3) adopts synchronous method biaxial stretching to replace step method biaxial stretching, namely the synchronous method biaxial stretching operation includes: firstly, preheating a polyvinyl alcohol casting sheet, and then simultaneously carrying out MD stretching and TD stretching; the conditions include: preheating temperature is 130 ℃, stretching temperature is 130 ℃, MD stretching ratio is 3.5 times, MD stretching rate is 300%/s, TD stretching ratio is 3.5 times, and TD stretching rate is 400%/s;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 17
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The process of example 4 was followed except that polyvinyl alcohol having an alcoholysis degree of 99mol%, a polymerization degree of 2000 and a particle size of 360 μm, which is available from Ningxia chemical Co., ltd, was used in place of the polyvinyl alcohol of example 4.
Finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 18
This example illustrates the polyvinyl alcohol film of the invention, its composition and method of preparation.
The method of embodiment 17 except that:
step (3) adopts synchronous method biaxial stretching to replace step method biaxial stretching, namely the synchronous method biaxial stretching operation includes: firstly, preheating a polyvinyl alcohol casting sheet, and then simultaneously carrying out MD stretching and TD stretching; the conditions include: preheating temperature is 130 ℃, stretching temperature is 130 ℃, MD stretching ratio is 3.5 times, MD stretching rate is 300%/s, TD stretching ratio is 3.5 times, and TD stretching rate is 400%/s;
finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Example 19
This example illustrates the polyvinyl alcohol film of the invention, its composition and preparation.
The process of example 18 was followed, except that polyvinyl alcohol having alcoholysis degree of 97mol%, polymerization degree of 1800 and particle size of 360 μm, which was obtained from Sichuan vinylon, a petrochemical plant, was used in place of the polyvinyl alcohol of example 16.
Finally, a film with an average thickness of 25 μm is obtained, which is composed of an upper surface layer, a core layer and a lower surface layer, and the raw materials of each layer are the polyvinyl alcohol composition of the embodiment. The properties of the obtained biaxially oriented film are shown in Table 2.
Comparative examples 1 to 5
According to the method described in example 1, except that equal parts by weight of the plasticizer DE1-DE5 were respectively used instead of E1, comparative examples 1-3 were broken during the biaxial stretching process and could not be stretched, and comparative examples 4-5 each finally obtained a film having an average thickness of 25 μm, which was composed of an upper skin layer, a core layer and a lower skin layer, each of which was made of the polyvinyl alcohol composition of this comparative example. The properties of the obtained biaxially oriented film are shown in Table 2.
Comparative examples 6 to 7
According to the method described in example 17, except that E4 was replaced by equal parts by weight of the plasticizers DE4 to DE5, respectively, films each having an average thickness of 25 μm were finally obtained, which consisted of an upper skin layer, a core layer and a lower skin layer, each of which was prepared from the polyvinyl alcohol composition of this comparative example. The properties of the obtained biaxially oriented film are shown in Table 2.
Comparative example 8
The process of example 1 was followed except that an equal weight part of unmodified polypropylene powder purchased from T30s of petrochemical and marine oil refining chemical ltd, china was used in place of the modified polypropylene particles PP-1;
finally, a film with the average thickness of 25 μm is obtained, which consists of an upper surface layer, a core layer and a lower surface layer, and the raw materials of all the layers are the polyvinyl alcohol composition of the comparative example. The properties of the obtained biaxially oriented film are shown in Table 2.
Comparative example 9
According to the method described in example 1, except that the polyvinyl alcohol composition prepared in step (1) was melt-extruded and directly cast into a film in the core layer extruder and the upper and lower surface layer extruders of a multi-layer extrusion casting machine of LCR400 manufactured by Labtech company of Sweden at a temperature of 110 to 140 ℃ and a casting chill roll temperature of 25 ℃ to directly obtain a cast film having an average thickness of 25 μm in step (2), and properties of the obtained cast film are shown in Table 2.
Comparative example 10
According to the method described in example 1, except that the polyvinyl alcohol film is obtained by extrusion blow molding using the top-blown film forming apparatus of dr.colin, germany, the polyvinyl alcohol composition prepared in step (1) is fed into the hopper of the extruder of the top-blown film forming apparatus, the raw material is sufficiently melted and plasticized by the extruder, and then extruded from the ring-shaped die of the head to form a melt film tube, and then blown by compressed air (blowing ratio is 2.5 times), and cooled by the air ring to form the blown polyvinyl alcohol film, wherein the film has a single-layer structure with an average thickness of 25 μm. The properties of the resulting blown film are shown in Table 2.
TABLE 2
The data in table 2 show that, by using the plasticizer provided in the present invention, a film of polyvinyl alcohol with a wide alcoholysis range can be prepared by biaxial stretching, and the prepared polyvinyl alcohol film has high strength, high barrier property and high light transmittance. Wherein, especially under the preferable mixture ratio, the tensile strength in the MD and TD directions is more than 100MPa, the light transmittance is more than 90 percent, and the oxygen permeability is 1.6cc/m 2 Day or less.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (27)
1. A biaxially oriented polyvinyl alcohol film, wherein said film comprises a polyvinyl alcohol composition comprising polyvinyl alcohol, a plasticizer, modified polypropylene, a lubricant, and optionally an auxiliary agent; the modified polypropylene is acrylate graft modified polypropylene; the plasticizer contains a component A, a component B and a component C; the component A is one or more of glycerol, glycol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, calcium chloride, copper sulfate and sodium acetate; the component C is water; the weight ratio of the polyvinyl alcohol to the plasticizer is 100:15-25; the weight ratio of the component A to the component B to the component C is 20-500:100:80-500 parts of;
the film is formed by biaxially stretching a polyvinyl alcohol cast sheet consisting of the polyvinyl alcohol composition, wherein the polyvinyl alcohol cast sheet is of a three-layer structure consisting of an upper surface layer, a core layer and a lower surface layer;
the weight ratio of the polyvinyl alcohol to the modified polypropylene is 100:10-40.
2. The film of claim 1, wherein the weight ratio of component a, component B, and component C in the polyvinyl alcohol composition is 30-300:100:100-300.
3. The film of claim 2, wherein the weight ratio of component a, component B, and component C in the polyvinyl alcohol composition is from 50-200:100:120-250.
4. A film according to any one of claims 1 to 3, wherein in the polyvinyl alcohol composition, component a is one or more of glycerol, polyethylene glycol having an average molecular weight of 200 to 400, and pentaerythritol;
the component B is one or more of magnesium chloride, magnesium nitrate and calcium chloride.
5. A film according to any one of claims 1 to 3, wherein the weight ratio of polyvinyl alcohol and lubricant in the polyvinyl alcohol composition is 100:0.5-5.
6. A film according to any one of claims 1 to 3, wherein the weight ratio of polyvinyl alcohol and lubricant in the polyvinyl alcohol composition is 100:1-3.
7. A film according to any one of claims 1 to 3, wherein the polyvinyl alcohol composition has a degree of alcoholysis of 80 to 99mol%, a degree of polymerization of 1500 or more and a particle size of 90 to 500. Mu.m.
8. A film according to any one of claims 1 to 3, wherein the polyvinyl alcohol composition has an alcoholysis degree of 80 to 90mol%, a polymerization degree of 1600 to 1800 and a particle size of 100 to 300 μm.
9. A film according to any one of claims 1 to 3, wherein the polyvinyl alcohol composition has an alcoholysis degree of 95 to 99mol%, a degree of polymerization of 1700 to 2500, and a particle size of 320 to 400 μm.
10. A film according to any one of claims 1 to 3, wherein in the polyvinyl alcohol composition the acrylate is one or more of methyl acrylate, ethyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate and glycidyl methacrylate.
11. The film according to any one of claims 1 to 3, wherein in the polyvinyl alcohol composition, the lubricant is one or more of a polyethylene glycol-based lubricant, a fluoropolymer-based lubricant, a silicone-based lubricant, a fatty alcohol-based lubricant, a fatty acid ester-based lubricant, a stearic acid amide-based lubricant, a fatty acid metal soap-based lubricant, an alkane and alkane oxide-based lubricant, and a micro-nano particle-based lubricant.
12. A film according to any one of claims 1 to 3, wherein in the polyvinyl alcohol composition, the auxiliary agent is one or more of an antioxidant, an acid acceptor, an antistatic agent and an antiblocking agent.
13. A method for preparing a biaxially oriented polyvinyl alcohol film, comprising:
(1) Providing a mixture of ingredients comprising the polyvinyl alcohol composition of any one of claims 1-12;
(2) Carrying out melt extrusion on the mixture and casting the mixture into a casting sheet to obtain a polyvinyl alcohol casting sheet;
(3) The cast piece of polyvinyl alcohol was biaxially stretched to form a film.
14. The method of claim 13, wherein step (1) comprises: firstly, mixing polyvinyl alcohol and a plasticizer, and then introducing modified polypropylene, a lubricant and an optional auxiliary agent;
wherein the mixing conditions of the polyvinyl alcohol and the plasticizer include: the temperature is 50-90 ℃ and the time is 0.5-4h.
15. The process of claim 13 or 14, wherein the melt extrusion temperature is 100-200 ℃; the casting quenching roller temperature of the casting sheet is 15-50 ℃.
16. The method of claim 13 or 14, wherein the cast sheet of polyvinyl alcohol is a single layer structure or a multi-layer structure.
17. The method of claim 13 or 14, wherein the cast sheet of polyvinyl alcohol is a three-layer structure consisting of an upper skin layer, a core layer, and a lower skin layer.
18. The method of claim 13 or 14, wherein the biaxial stretching comprises simultaneous or stepwise stretching;
the synchronous Faraday stretching comprises the steps of preheating a polyvinyl alcohol casting sheet, and simultaneously stretching in an MD and a TD mode; the conditions for the simultaneous stretching include: the stretching temperature is 120-170 ℃, the MD stretching ratio is more than 3 times, the TD stretching ratio is more than 3 times, the MD stretching rate is more than 300%/s, and the TD stretching rate is more than 300%/s;
the step-wise stretching comprises: preheating a polyvinyl alcohol casting sheet, then performing MD stretching, then preheating and then performing TD stretching; the conditions of the step-by-step drawing comprise: the MD stretching temperature is 80-100 ℃, the TD stretching temperature is 120-200 ℃, the MD stretching ratio is more than 3 times, the TD stretching ratio is more than 3 times, the MD stretching rate is more than 100%/s, and the TD stretching rate is more than 100%/s.
19. The method of claim 13 or 14, further comprising annealing the resulting film after step (3), the annealing being at a temperature of 180-200 ℃.
20. A polyvinyl alcohol film produced by the method of any one of claims 13-19.
21. The polyvinyl alcohol film according to claim 20, wherein the polyvinyl alcohol film has an MD tensile strength of 45MPa or more; TD tensile strength is more than 55MPa; the light transmittance is more than 90%; the oxygen permeability is 1.6cc/m 2 Day or less.
22. The polyvinyl alcohol film according to claim 21, wherein the polyvinyl alcohol film has an MD tensile strength of 60MPa or more.
23. The polyvinyl alcohol film according to claim 21, wherein the polyvinyl alcohol film has an MD tensile strength of 100MPa or more.
24. The polyvinyl alcohol film according to claim 21, wherein the TD tensile strength of the polyvinyl alcohol film is 70MPa or more.
25. The polyvinyl alcohol film according to claim 21, wherein the TD tensile strength of the polyvinyl alcohol film is 100MPa or more.
26. The polyvinyl alcohol film according to claim 21, wherein the polyvinyl alcohol film has a light transmittance of 92-94%.
27. The polyvinyl alcohol film of claim 21, wherein the polyvinyl alcohol film has an oxygen transmission rate of 1.4cc/m 2 Day or less.
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| CN113088019B (en) * | 2020-01-09 | 2022-12-09 | 中国石油化工股份有限公司 | Thermoplastic low-alcoholysis-degree polyvinyl alcohol film for barrier and preparation method and application thereof |
| CN113201160B (en) * | 2020-02-01 | 2022-08-19 | 中国石油化工股份有限公司 | Humidity-control barrier composite film and preparation method and application thereof |
| CN112300426A (en) * | 2020-10-26 | 2021-02-02 | 广东安德力新材料有限公司 | Preparation method of polypropylene film layer capable of eliminating stress residue |
| CN114437481B (en) * | 2020-10-30 | 2023-02-24 | 中国石油化工股份有限公司 | Polyvinyl alcohol composition, polyvinyl alcohol film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405653A (en) * | 1994-02-28 | 1995-04-11 | E. I. Du Pont De Nemours And Company | Poly(vinyl alcohol)starch blends for textile sizes with improved ability to be desized |
| CN101889052A (en) * | 2007-12-05 | 2010-11-17 | 可乐丽股份有限公司 | Polyvinyl alcohol fiber-containing polyolefin resin composition and molded article thereof |
| CN102532595A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | Compounded plasticizer for thermoplastic processing and method for plasticizing polyvinyl alcohol |
| CN102604294A (en) * | 2012-03-13 | 2012-07-25 | 朱春英 | Stretched PVA (polyvinyl alcohol) film and preparation method for same |
| CN103242612A (en) * | 2013-05-28 | 2013-08-14 | 上海博疆新材料科技有限公司 | Polyvinyl alcohol composition and application thereof |
| CN107266761A (en) * | 2016-04-07 | 2017-10-20 | 中国石油化工集团公司 | A kind of thermoplastic polyvinyl alcohol water resistance compound and preparation method thereof |
-
2017
- 2017-10-30 CN CN201711036162.0A patent/CN109721905B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5405653A (en) * | 1994-02-28 | 1995-04-11 | E. I. Du Pont De Nemours And Company | Poly(vinyl alcohol)starch blends for textile sizes with improved ability to be desized |
| CN101889052A (en) * | 2007-12-05 | 2010-11-17 | 可乐丽股份有限公司 | Polyvinyl alcohol fiber-containing polyolefin resin composition and molded article thereof |
| CN102532595A (en) * | 2011-12-23 | 2012-07-04 | 四川大学 | Compounded plasticizer for thermoplastic processing and method for plasticizing polyvinyl alcohol |
| CN102604294A (en) * | 2012-03-13 | 2012-07-25 | 朱春英 | Stretched PVA (polyvinyl alcohol) film and preparation method for same |
| CN103242612A (en) * | 2013-05-28 | 2013-08-14 | 上海博疆新材料科技有限公司 | Polyvinyl alcohol composition and application thereof |
| CN107266761A (en) * | 2016-04-07 | 2017-10-20 | 中国石油化工集团公司 | A kind of thermoplastic polyvinyl alcohol water resistance compound and preparation method thereof |
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