CN109181182A - A kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type - Google Patents
A kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
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Abstract
The present invention relates to degradable film fields, and in particular to arrives a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type.The polyvinyl alcohol full-biodegradable film, by weight, preparing raw material includes: 100 parts of polyvinyl alcohol, the first plasticizer of 10-20 part, 5-20 the second plasticizer of part.The preparation-obtained resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type of the present invention not only can effectively inhibit migration of plasticizer in product, and product has excellent water resistance.
Description
Technical field
The invention belongs to degradable film fields, more particularly it relates to which a kind of resistance to migration polyvinyl alcohol of environment-friendly type is complete
Biodegradable film.
Background technique
With the enhancing of national environmental consciousness, clean manufacturing, resources sustainable development consciousness, dropped using environmental-friendly
The material of solution is to reduce " white pollution ", it has also become one of the research hotspot of domestic and international Material Field.Polyvinyl alcohol (PVA) is one
Kind artificial synthesized water soluble polymer, with excellent physical such as good film forming, elasticity, high-tensile
Can, by extensive concern both domestic and external.
Current commercialized polyvinyl alcohol Biodegradable films add in order to increase the flexibility and elasticity of polyvinyl alcohol more
Glycerol, caprolactam or multicondensed ethylene glycol etc polyalcohol and linear polyester are as plasticizer.But this kind of plasticizer, is easy to by rain
Water washes away loss, and effective time is too short, it is easier that product surface softens, tacky or even fragmentation, and plasticizer loss is to ring
It is a kind of potential hidden danger to environment and human health in border.
Now studies have found that having been examined in the substances such as grain, toy for children, drinking-water, atmosphere, steamer and aircraft and environment
The different plasticizer of content out.In recent years, the restricted environmental regulation of plasticizer has been put into effect in succession both at home and abroad.Thus exploitation one
The kind resistance to migration polyvinyl alcohol full-biodegradable film of novel environment-friendly has become very important goal in research.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type,
By weight, preparing raw material includes: 100 parts of polyvinyl alcohol, the first plasticizer of 10-20 part, 5-20 the second plasticizer of part.
As a kind of perferred technical scheme, the degree of polymerization of the polyvinyl alcohol is 300-5000, alcoholysis degree >=98%.
As a kind of perferred technical scheme, first plasticizer is hyper-branched polyester.
As a kind of perferred technical scheme, the hyper-branched polyester is end carboxyl super branched polyester.
As a kind of perferred technical scheme, the monomer of the end carboxyl super branched polyester is citric acid and/or malic acid.
As a kind of perferred technical scheme, second plasticizer is polymer polyatomic alcohol.
As a kind of perferred technical scheme, the weight ratio of first plasticizer and the second plasticizer is 1-2:1.
As a kind of perferred technical scheme, by weight, the preparation of the polyvinyl alcohol full-biodegradable film is former
Material further include: 1-2 parts of crosslinking agents, 1-3 parts of lubricants, 1-5 parts of heat stabilizers, 1-3 parts of tart flavour scavengers.
As a kind of perferred technical scheme, by weight, the preparation of the polyvinyl alcohol full-biodegradable film is former
Material further include: 10-25 parts of crown ether compounds.
As a kind of perferred technical scheme, the crown ether compound is benzo-crown ether.
As a kind of perferred technical scheme, the benzo-crown ether be selected from phendioxin 2- crown ether -4, phendioxin 5- crown ether -5,
Benzo-18-crown-6, benzo -21- crown ether -7, dibenzo -12- crown ether -4, dibenzo -15- crown ether -5, dibenzo -18- hat
One in ether -6, crown ether -7 dibenzo -21- and their own methyl, ethyl, isopropyl or tert-butyl substituent
Kind is a variety of.
It, not only can be with the utility model has the advantages that the prepared by the method resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type
It is effective to inhibit migration of plasticizer in product, and the first plasticizer used is that biological basic ring protects material, meets this polyethylene
The environmentally protective requirement of alcohol full-biodegradable film.In addition to this, the resistance to migration polyvinyl alcohol of environment-friendly type provided by the invention is complete
Biodegradable film is flexible smoothly, oil resistant, solvent resistant, abrasion performance, barrier properties for gases are good, has excellent water resistance.
Specific embodiment
It is further clear, complete that the technical characteristic work in technical solution is provided to the present invention With reference to embodiment
Description, not to the limitation of its protection scope.
Word " preferred ", " preferred " in the present invention etc. refer to, can provide in some cases certain beneficial to effect
The embodiment of the present invention of fruit.However, other embodiments are also likely to be preferred under identical circumstances or in the case of other
's.In addition, do not imply that other embodiments are unavailable to the statement of one or more preferred embodiments, be also not intended to by
Other embodiments exclude except the scope of the present invention.
When a numberical range disclosed herein, above range is considered as continuously, and the minimum value including the range and most
Big value and each value between this minimum value and maximum value.Further, when range refers to integer, including the model
Each integer between minimum value and maximum value enclosed.In addition, when providing multiple range Expressive Features or characteristic, Ke Yihe
And the range.In other words, unless otherwise specified, otherwise all ranges disclosed herein are understood to include and are wherein included into
Any and all subrange.For example, should be regarded as including between minimum value 1 and maximum value 10 from the specified range of " 1 to 10 "
Any and all subrange.The Exemplary range of range 1 to 10 include but is not limited to 1 to 6.1,3.5 to 7.8,5.5 to
10 etc..
To solve the above-mentioned problems, the present invention provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type,
By weight, preparing raw material includes: 100 parts of polyvinyl alcohol, the first plasticizer of 10-20 part, 5-20 the second plasticizer of part.
In a preferred embodiment, by weight, the preparation of the polyvinyl alcohol full-biodegradable film is former
Material further include: 1-2 parts of crosslinking agents, 1-3 parts of lubricants, 1-5 parts of heat stabilizers, 1-3 parts of tart flavour scavengers.
In a kind of preferred embodiment, by weight, the preparation of the polyvinyl alcohol full-biodegradable film
Raw material further include: 10-25 parts of crown ether compounds, wherein crown ether compound is benzo-crown ether.
In a kind of preferred embodiment, by weight, the preparation of the polyvinyl alcohol full-biodegradable film
Raw material includes: 100 parts of polyvinyl alcohol, the first plasticizer of 10-20 part, the second plasticizer of 5-20 part, 1-2 parts of crosslinking agents, 1-3 parts of profits
Lubrication prescription, 1-5 part heat stabilizer, 1-3 parts of tart flavour scavengers, 10-25 parts of crown ether compounds.
Polyvinyl alcohol
Heretofore described polyvinyl alcohol is important industrial chemicals, degree of polymerization 300-5000, alcoholysis degree >=98%.
The degree of polymerization is to measure the index of polymer molecule size.On the basis of number of repeat unit, i.e. polymer macromolecule chain
Upper contained number of repeat unit purpose average value, is indicated with n；It is on the basis of structural unit number, i.e., contained on polymer macromolecule chain
Single structure number of unit.Since high polymer is the mixture of the homologue of different molecular weight mostly, so the polymerization of high polymer
Degree refers to its average degree of polymerization.Polymer is the mixture institute group of the homologue by one group of different polymerization degree and different structure form
At, therefore the degree of polymerization is unified meter average value.
Alcoholysis degree refers to that hydroxyl in the product obtained after alcoholysis accounts for the percentage of original group.
In some embodiments, the degree of polymerization of the polyvinyl alcohol is 300-5000.
Specifically, the degree of polymerization of the polyvinyl alcohol be 300,500,1700,2400,2600,3000,3200,3500,
4000、4500、5000。
When the degree of polymerization is less than 300, intensity after film forming and solvent resistance reduce, and when the degree of polymerization is greater than 5000, viscosity
Excessively high, processing performance reduces.It is needed with the usually used high strength poly vinyl alcohol of Material Field with hot water resistance in industry, because
And the polyvinyl alcohol that alcoholysis degree need to be used to be more than or equal to 98%.
Polyvinyl alcohol is bought from KURARAY company, the degree of polymerization 300, alcoholysis degree >=98%, model in the application are as follows:
KURARAY POVAL 3-98；The degree of polymerization is 500, alcoholysis degree >=98%, model are as follows: KURARAY POVAL 5-98；The degree of polymerization
It is 1700, alcoholysis degree >=98%, model are as follows: KURARAY POVAL 28-98；The degree of polymerization is 2400, alcoholysis degree >=98%, model
Are as follows: KURARAY POVAL 60-98.
First plasticizer
Heretofore described plasticizer is the high molecular material auxiliary agent being industrially widely used, and is added in plastic processing
Add this substance, its flexibility can be made to enhance, be easily worked, legal can be used for industrial use, be used primarily in high molecular material
In.
In some embodiments, first plasticizer is hyper-branched polyester.
In a preferred embodiment, the hyper-branched polyester is end carboxyl super branched polyester.
In a kind of preferred embodiment, the monomer of the end carboxyl super branched polyester is citric acid and/or apple
Acid.
Hyper-branched polyester is that one kind is different from conventional linear polyester, in highly branched structure, branching repeat unit
New polymers containing ester group.It is synthesized in dissaving polymer development process compared with early, application is strong, synthesis technology is mature
A kind of typical dissaving polymer and dissaving polymer family in one of most important member, wherein carboxyl end group is super
Contain a large amount of pendant carboxylic groups in the skeleton end of branched polyester.
In a preferred embodiment, first plasticizer is to be using citric acid as the hyper-branched polyester of monomer
It is prepared using citric acid as raw material by polycondensation reaction, step includes:
S1. citric acid 6g is weighed, is dissolved in 15mL tetrahydrofuran solution；
S2. above-mentioned system is passed through nitrogen protection, stirs 30min after 3mL thionyl chloride is added under ice bath, is added later
Pyridine continues to stir 20min；
S3. system is moved in microwave synthesizer after and is reacted.Product is divided into upper layer and lower layer, and supernatant liquor is tetrahydro
Tetrahydrofuran solution, lower layer's glassy yellow thick liquid are hyper-branched polyester.Lower liquid is dialysed, remove residual solvent to get
Target compound.
In a preferred embodiment, first plasticizer is to be using malic acid as the hyper-branched polyester of monomer
It is prepared using malic acid as raw material by polycondensation reaction, step includes:
A. malic acid 6g is weighed, is dissolved in 15mL tetrahydrofuran solvent, system is passed through nitrogen protection；
B. by 1.5g N, N- dicyclohexylcarbodiimide is dissolved in 15mL n,N-Dimethylformamide, will under ice bath
In its system for being added to step A；
C. 18h is stirred at room temperature, filters out pale precipitation later, filtrate is distilled to obtain faint yellow oily viscous fluid
Body, as target compound.
The application has found that film provided by the invention has preferable plasticising performance, and will not generate small molecule precipitation
Phenomenon.Inventor speculates, the possible reason is present invention employs hyper-branched polyester, compared to common linear polymer,
It has the three-dimensional molecular structure of spheroidal, and the presence of a large amount of branches increases end base density, and terminal segments have more
Big free volume.In addition, inventor also found hyper-branched polyester not only, to can effectively improve polyvinyl alcohol complete biodegradable thin
The water resistance of film, it is also possible that its tensile strength and elongation at break are further promoted.Inventor thinks and hyperbranched poly
It is related that a large amount of pendant carboxylic group is contained in ester skeleton end, when a large amount of pendant carboxylic group is contained in hyper-branched polyester skeleton end,
It can be further crosslinked with the PVA being crosslinked.But when hyper-branched polyester is used alone, film brittleness is higher, the present inventor
When being surprised to find that compound the first plasticizer with the second plasticizer, the flexibility of film is significantly improved.
Second plasticizer
In some embodiments, second plasticizer is polymer polyatomic alcohol, is selected from polyether polyol, polyester polyols
Alcohol, polycarbonate polyol, epoxy polyol, vegetable oil polyol, polyolefin polyhydric alcohol, acrylic polyol, polyurethane are more
One of pure and mild vinyl monomer modified polyalcohol of member is a variety of.
As the example of polyether polyol, including but not limited to: polypropylene glycol, polytetramethylene ether diol.
As the example of polyester polyol, it can enumerate and use low molecular weight polyols (preferably binary under the conditions of known
Alcohol) resulting condensation polymer is reacted with polyacid, wherein low molecular weight polyols can be ethylene glycol, propylene glycol, 1,3-PD,
1,4- butanediol, 1,3 butylene glycol, 1,2- butanediol, 1,5- pentanediol, 1,6-HD, neopentyl glycol, alkane (C7-C22)
Glycol, diethylene glycol (DEG), triethylene glycol, dipropylene glycol, 3- methyl-1,5- pentanediol, alkane -1,2- glycol (C17-C20), 1,3- or 1,
4- cyclohexanedimethanol and their mixture, 1,4- cyclohexanediol, hydrogenated bisphenol A, 1,4- dihydroxy -2- butylene, 2,6- bis-
The dihydric alcohols such as methyl-1-octene-3,8- glycol, bisphenol-A；The trihydroxylic alcohols such as glycerine, trimethylolpropane；Tetramethylol methane
The tetrahydroxylic alcohols such as (pentaerythrite), diglycerol；The pentabasis alcohols such as xylitol；Sorbierite, mannitol, allitol, iditol, winged euonymus
The hexahydroxylic alcohols such as alcohol, altritol, inositol, dipentaerythritol；The heptabasic alcohols such as mannoheptitol；Eight yuan of alcohol such as sucrose etc..
As the example of polycarbonate polyol, can enumerate using above-mentioned low molecular weight polyols (preferably dihydric alcohol) as
The ring-opening polymerization polymer of the ethylene carbonate of initiator, and by 1,4-butanediol, 1,5-PD, 3- methyl-1,5- pentanediol
Or the dihydric alcohols such as 1,6-HD and ring-opening polymerization polymer are copolymerized resulting amorphous poly carbonate polyol etc..
As the example of epoxy polyol, can enumerate through above-mentioned low molecular weight polyols and epichlorohydrin, Beta-methyl table
The epoxy polyol that the multifunctional halohydrin such as chloropharin reacts.
As the example of vegetable oil polyol, the vegetable oil etc. containing hydroxyl such as castor oil, coconut oil can be enumerated；It can be with
Enumerate castor oil polyhydric alcohol or by castor oil polyhydric alcohol and the resulting ester modified castor oil polyhydric alcohol of polypropylene polyol reaction
Deng.
As the example of polyolefin polyhydric alcohol, polyvinyl alcohol, polyethylene glycol, polybutadiene polyol, part can be enumerated
Saponified ethylene-vinyl acetate copolymer etc..
As the example of acrylic polyol, the acrylate by making that there is hydroxyl can be enumerated, and can with have
Copolymer obtained from the copolymerizable vinyl monomer copolymerization of the acrylic ester copolymer of hydroxyl.
In a preferred embodiment, second plasticizer is polytetramethylene ether diol.
Polytetramethylene ether diol described herein, No. CAS is 25190-06-1, is bought from traditional Chinese medicines chemical reagent.
Crosslinking agent
Heretofore described crosslinking agent is used primarily in high molecular material.Since the molecular structure of high molecular material is as one
Long line, intensity is low when not being crosslinked, easily break and no elasticity, the effect of crosslinking agent are exactly to produce between the molecule of line style
Biochemical key, is connected with each other linear molecule, forms reticular structure.
In some embodiments, the crosslinking agent is selected from: boric acid, oxalic acid, urea, maleic anhydride, citric acid, inclined benzene three
It is acid anhydrides, phthalic anhydride, 1,6- adipic acid, Boratex, organic borate cross-linker, organic boron zirconium cross linking agent, diisocyanate, different
One of cyanate, epoxychloropropane, polyacrylic acid and maleic acid are a variety of.
In a preferred embodiment, the crosslinking agent is borax.
Lubricant
Lubricant has a variety of efficiency in the actual processing of plastics, such as when being kneaded, calendering being processed, can prevent from polymerizeing
Object adhesion barrel, inhibits frictional heat generation, reduces and be kneaded torque and load, to prevent the heat deterioration of polymer material.It is squeezing out
When molding, mobility can be improved, improve the adhesion of polymer material and barrel and mold, prevent and reduce retentate, in addition also
The appearance and gloss of film can be improved.Lubricant can also play melting promotor, prevent adhesion and prevent quiet other than improving mobility
The effects of electric agent, slipping agent.
In some embodiments, the lubricant is able to use known lubricant, including but not limited to: liquid stone
It is wax, paraffin, polyethylene wax, lauric acid, myristic acid, palmitinic acid, stearic acid, arachidic acid, behenic acid, montanic acid, hexanol, pungent
Alcohol, hexadecanol, octadecanol, behenyl alcohol, 1,2- ethylene glycol, glycerine, polyglycerol, geoceric acid stearyl alcohol ester, behenic acid
Shan Yu ester, pentaerythrite tristearate, pentaerythritol tetrastearate, glycerol monostearate, glycerine Dan behenic acid
It is ester, stearmide, palmitamide, oleamide, methylene bis stearamide, ethylenebisstearamide, calcium stearate, hard
Resin acid zinc, magnesium stearate, lignite wax, silicone oil etc..
In a preferred embodiment, the lubricant is calcium stearate.
Heat stabilizer
Heat stabilizer is a kind of object that polymeric material causes degradation and addition under heat and the effects of shearing force in order to prevent
Matter, for poor heat resistance, the heat resistance of the polymer is can be improved in wherein addition heat stabilizer in the polymer for being easy degradation.
In some embodiments, the heat stabilizer is able to use known heat stabilizer, including but not limited to: alkaline earth
Metal chloride, hydrotalcite, calcium-zinc-base, epoxy group, organic phosphorous acid ester group, beta-diketon base, zeolite base, mercapto tinbase, Malaysia
Sour tinbase, lauric acid tinbase and barium-zinc based stabilizer etc..
In a preferred embodiment, the heat stabilizer is calcium chloride.
Tart flavour scavenger
In some embodiments, the tart flavour scavenger is alkaline earth metal hydroxide and/or carbonate.
As the example of alkaline earth oxide, including but not limited to: magnesium hydroxide, calcium hydroxide, barium hydroxide etc..
As the example of carbonate, including but not limited to: calcium carbonate, sodium carbonate, sodium bicarbonate, manganese carbonate, zinc carbonate, carbon
Sour potassium, saleratus, magnesium carbonate, ammonium hydrogen carbonate, cadmium carbonate etc..
In a preferred embodiment, the tart flavour scavenger is magnesium hydroxide.
Crown ether compound
Inventor is surprised to find that crown ether compound is added in the feed not only can further suppress small molecule precipitation
The phenomenon that, and the water resistance of film is also improved.Inventor speculates, it may be possible to due to containing cavity knot in crown ether molecule
Structure adds it in formula, can form inclusion compound, while the addition of crown ether compound with the substance of easy precipitation, make
Plasticizer is formed by inclusion compound with it and comes into full contact with polyvinyl alcohol so that the interaction of plasticizer and polyvinyl alcohol is more
Step up close abundant.
In some embodiments, the crown ether compound is benzo-crown ether.
In a preferred embodiment, the benzo-crown ether be selected from phendioxin 2- crown ether -4, phendioxin 5- crown ether -5,
Benzo-18-crown-6, benzo -21- crown ether -7, dibenzo -12- crown ether -4, dibenzo -15- crown ether -5, dibenzo -18- hat
One in ether -6, crown ether -7 dibenzo -21- and their own methyl, ethyl, isopropyl or tert-butyl substituent
Kind is a variety of.
In a preferred embodiment, the crown ether compound is dibenzo-18-crown-6 (DB18C6).
Crown ether compound described herein is purchased from traditional Chinese medicines chemical reagent, wherein phendioxin 5- crown ether -5, No. CAS
For 14098-44-3；Benzo-18-crown-6, No. CAS is 14098-24-9；Dibenzo-18-crown-6 (DB18C6), No. CAS is 14187-
32-7；18- crown ether -6, No. CAS is 17455-13-9；Azepine 15- crown ether -5, No. CAS is 66943-05-3.
The present invention is specifically described below by embodiment, in addition, if without other explanations, it is raw materials used to be all
It is commercially available.
Embodiment
Embodiment 1
Embodiment 1 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 10 part of first plasticizer, 5 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 300, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of citric acid
It should be prepared, step includes:
S1. citric acid 6g is weighed, is dissolved in 15mL tetrahydrofuran solution；
S2. above-mentioned system is passed through nitrogen protection, stirs 30min after 3mL thionyl chloride is added under ice bath, is added later
Pyridine continues to stir 20min；
S3. system is moved in microwave synthesizer after and is reacted.Product is divided into upper layer and lower layer, and supernatant liquor is tetrahydro
Tetrahydrofuran solution, lower layer's glassy yellow thick liquid are hyper-branched polyester.Lower liquid is dialysed, remove residual solvent to get
Target compound.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first polyvinyl alcohol water solution and 1 part of borax are pre-mixed, are then added 10 part first
Plasticizer uniformly mixes, and 5 part of second plasticizer, 1 part of calcium stearate, 1 part of calcium chloride, 1 part of magnesium hydroxide, 10 parts of benzene are added later
And -18- crown ether -6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 2
Embodiment 2 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 20 part of first plasticizer, 20 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 2400, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of citric acid
It should be prepared, the preparation method is the same as that of Example 1.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first polyvinyl alcohol water solution and 2 parts of boraxs are pre-mixed, are then added 20 part first
Plasticizer uniformly mixes, and 20 part of second plasticizer, 3 parts of calcium stearates, 5 parts of calcium chloride, 3 parts of magnesium hydroxides, 25 parts are added later
Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 3
Embodiment 3 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 12 part of first plasticizer, 7 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 500, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of citric acid
It should be prepared, the preparation method is the same as that of Example 1.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.2 parts of boraxs are pre-mixed, are then added 12 part first
Plasticizer uniformly mixes, and 7 part of second plasticizer, 1.5 parts of calcium stearates, 2 parts of calcium chloride, 1.5 parts of magnesium hydroxides, 15 are added later
Part Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 4
Embodiment 4 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 18 part of first plasticizer, 15 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of citric acid
It should be prepared, the preparation method is the same as that of Example 1.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.8 parts of boraxs are pre-mixed, are then added 18 part first
Plasticizer uniformly mixes, later be added 15 part of second plasticizer, 2.5 parts of calcium stearates, 4 parts of calcium chloride, 2.5 parts of magnesium hydroxides,
20 parts of Benzo-18-crown-6s are sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 5
Embodiment 5 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of citric acid
It should be prepared, the preparation method is the same as that of Example 1.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 6
Embodiment 6 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, step includes:
A. malic acid 6g is weighed, is dissolved in 15mL tetrahydrofuran solvent, system is passed through nitrogen protection；
B. by 1.5g N, N- dicyclohexylcarbodiimide is dissolved in 15mL n,N-Dimethylformamide, will under ice bath
In its system for being added to step A；
C. 18h is stirred at room temperature, filters out pale precipitation later, filtrate is distilled to obtain faint yellow oily viscous fluid
Body, as target compound.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 7
Embodiment 7 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using citric acid as the hyper-branched polyester of monomer and using malic acid as the hyperbranched poly of monomer
Ester 1:1 compounding, described using citric acid as the hyper-branched polyester of monomer, the preparation method is the same as that of Example 1, described using malic acid as monomer
Hyper-branched polyester, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 8
Embodiment 8 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Phendioxin 5- crown ether -5 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Embodiment 9
Embodiment 9 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Dibenzo-18-crown-6 (DB18C6) is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 1
Comparative example 1 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 10 part of second plasticizer.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, 10 part second is added later
Plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides are sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 2
Comparative example 2 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 10 part of second plasticizer.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, 10 part second is added later
Plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts of dibenzo-18-crown-6 (DB18C6)s are sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 3
Comparative example 3 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is superbrnaching end-hydroxy polyester, product grade are as follows: H101 is bought from Wuhan hyperbranched resin
Co., Ltd.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Dibenzo-18-crown-6 (DB18C6) is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 4
Comparative example 4 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is polylactic acid, No. CAS are as follows: 26100-51-6, purchase is from traditional Chinese medicines chemical reagent.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
18- crown ether -6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 5
Comparative example 5 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and it is sufficiently mixed that 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts of 18- crown ethers -6 are added later
It closes uniform；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 6
Comparative example 6 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is glycerol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
18- crown ether -6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 7
Comparative example 7 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and it is sufficiently mixed that 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides are added later
It closes uniform；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 8
Comparative example 8 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
18- crown ether -6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 9
Comparative example 9 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described poly-
The raw material for preparing of vinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Azepine 15- crown ether -5 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 10
Comparative example 10 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described
The raw material for preparing of polyvinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 5 part of first plasticizer, 10 part of second plasticising
Agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 5 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Dibenzo-18-crown-6 (DB18C6) is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 11
Comparative example 11 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described
The raw material for preparing of polyvinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 40 part of first plasticizer, 10 part of second increasing
Mould agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 40 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 18 parts are added later
Dibenzo-18-crown-6 (DB18C6) is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 12
Comparative example 12 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described
The raw material for preparing of polyvinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second increasing
Mould agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 5 part two are added later
Benzo-18-crown-6 is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Comparative example 13
Comparative example 13 provides a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, by weight, described
The raw material for preparing of polyvinyl alcohol full-biodegradable film includes: 100 parts of polyvinyl alcohol, 15 part of first plasticizer, 10 part of second increasing
Mould agent.
The polyvinyl alcohol degree of polymerization is 1700, alcoholysis degree >=98%.
First plasticizer is using malic acid as the hyper-branched polyester of monomer, is anti-by polycondensation by raw material of malic acid
It should be prepared, preparation method is the same as embodiment 6.
Second plasticizer is polytetramethylene ether diol.
The preparation method of the polyvinyl alcohol full-biodegradable film the following steps are included:
(1) by weight, first 100 parts of polyvinyl alcohol and 1.5 parts of boraxs are pre-mixed, are then added 15 part first
Plasticizer uniformly mixes, and 10 part of second plasticizer, 2 parts of calcium stearates, 3 parts of calcium chloride, 2 parts of magnesium hydroxides, 40 parts are added later
Dibenzo-18-crown-6 (DB18C6) is sufficiently mixed uniformly；
(2) mixture of above-mentioned steps (1) is added directly into and carries out being extruded into thin slice in double screw extruder, squeezed out
Temperature is 170 DEG C, screw speed 150rpm；
(3) roll-in, be distracted into the film with a thickness of 20 μm, and humidify, cut and wind.Film is adopted after roll-in, traction
With cooling humidifier, then wound.
Performance evaluation
To the PVA full-biodegradable film that embodiment and comparative example in the present invention provides, referring to GB/T1040-92 " plastics
Erichsen test method " standard obtains the parameters such as tensile strength (MPa), elongation at break (%)；Mobility is referring to ISO176-
2005 active carbon adsorptions are measured, and at 25 DEG C, constant temperature perseverance tests plasticizer in PVA test piece after doing 7d, 15d, 30d respectively
Migration loss.
1 performance test table of table
By continuing to optimize to experiment condition, embodiment 9 is most preferred embodiment, at 25 DEG C, the migration surveyed after 30 days
Rate is only 0.6%, and tensile strength and elongation at break are superior to other embodiments and comparative example.By comparative example 1 and embodiment 9
It compares, at 25 DEG C, the mobility surveyed after 30 days is 2.3%, illustrates to be not added with the first plasticizer and crown ether-like
Closing object significantly reduces the resistance to migration of film.By comparing comparative example 5, discovery is not added with the second plasticizer, so that film is resistance to
Migration and water resistance equally significantly reduce.
Claims (10)
1. a kind of resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type, which is characterized in that by weight, prepare raw material packet
It includes: 100 parts of polyvinyl alcohol, the first plasticizer of 10-20 part, 5-20 the second plasticizer of part.
2. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that described poly-
The degree of polymerization of vinyl alcohol is 300-5000, alcoholysis degree >=98%.
3. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that described
One plasticizer is hyper-branched polyester.
4. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 3, which is characterized in that described super
Branched polyester is end carboxyl super branched polyester.
5. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 4, which is characterized in that the end
The monomer of carboxyl super branched polyester is citric acid and/or malic acid.
6. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that described
Two plasticizer are polymer polyatomic alcohol.
7. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that described
The weight ratio of one plasticizer and the second plasticizer is 1-2:1.
8. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that by weight
Part meter, the polyvinyl alcohol full-biodegradable film prepare raw material further include: 1-2 parts of crosslinking agents, 1-3 parts of lubricants, 1-5 parts
Heat stabilizer, 1-3 parts of tart flavour scavengers.
9. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 1, which is characterized in that by weight
Part meter, the polyvinyl alcohol full-biodegradable film prepare raw material further include: 10-25 parts of crown ether compounds.
10. the resistance to migration polyvinyl alcohol full-biodegradable film of environment-friendly type according to claim 9, which is characterized in that described
Crown ether compound is benzo-crown ether.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280226A (en) * | 2020-10-19 | 2021-01-29 | 中国石油化工股份有限公司 | Polyvinyl alcohol optical film and preparation method thereof |
| CN114591581A (en) * | 2020-12-03 | 2022-06-07 | 中国石油化工股份有限公司 | Low-odor polyvinyl alcohol thermoplastic resin and preparation method thereof |
| CN114605821A (en) * | 2022-03-21 | 2022-06-10 | 上海金发科技发展有限公司 | Bio-based nylon material and preparation method thereof |
| CN114736404A (en) * | 2022-04-01 | 2022-07-12 | 四川大学 | Polyvinyl alcohol product capable of remarkably improving plasticizer migration and preparation method thereof |
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| CN101864132A (en) * | 2010-05-26 | 2010-10-20 | 四川大学 | Fusion preparation method of polyvinyl alcohol film |
| CN103724901A (en) * | 2014-01-03 | 2014-04-16 | 北京化工大学常州先进材料研究院 | Preparation method of fully degradable biological mulch film |
| CN104356569A (en) * | 2014-11-28 | 2015-02-18 | 云南云天化股份有限公司 | Polyvinyl alcohol (PVA) film and preparation method thereof, and polaroid |
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| CN101864132A (en) * | 2010-05-26 | 2010-10-20 | 四川大学 | Fusion preparation method of polyvinyl alcohol film |
| CN103724901A (en) * | 2014-01-03 | 2014-04-16 | 北京化工大学常州先进材料研究院 | Preparation method of fully degradable biological mulch film |
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Cited By (4)
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| CN112280226A (en) * | 2020-10-19 | 2021-01-29 | 中国石油化工股份有限公司 | Polyvinyl alcohol optical film and preparation method thereof |
| CN114591581A (en) * | 2020-12-03 | 2022-06-07 | 中国石油化工股份有限公司 | Low-odor polyvinyl alcohol thermoplastic resin and preparation method thereof |
| CN114605821A (en) * | 2022-03-21 | 2022-06-10 | 上海金发科技发展有限公司 | Bio-based nylon material and preparation method thereof |
| CN114736404A (en) * | 2022-04-01 | 2022-07-12 | 四川大学 | Polyvinyl alcohol product capable of remarkably improving plasticizer migration and preparation method thereof |
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| CN109181182B (en) | 2021-05-28 |
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