CN109825016A - A kind of biodegrade PVA stretch wrap film and preparation method thereof - Google Patents
A kind of biodegrade PVA stretch wrap film and preparation method thereof Download PDFInfo
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- CN109825016A CN109825016A CN201910070484.XA CN201910070484A CN109825016A CN 109825016 A CN109825016 A CN 109825016A CN 201910070484 A CN201910070484 A CN 201910070484A CN 109825016 A CN109825016 A CN 109825016A
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Abstract
The invention belongs to packaging film fields, specially a kind of biodegrade PVA stretch wrap film and preparation method thereof, the raw material group of the stretch wrap film becomes PVA, polyalcohols plasticizer, deionized water, processing aid and modifying agent, it is that will have biodegradable modified PVA material, it is modified by fusion plastification, using a kind of insoluble winding film of room temperature of the method preparation of dry method melting extrusion, the PVA stretch wrap film of the method for the invention preparation is not only degradable, but also there are also good physical property and tacks.Raising with people to environmental protection consciousness, the packaging material for reducing white pollution continue to bring out, and the present invention be directed to the research and development of this market demand.Present invention process is simple, cost is relatively low, and normal-temperature water is insoluble；Overcoming the secondary polycondensation of PVA in compost degradation process influences disintegration rate；Processing fluidity is excellent, is advantageously implemented fusion plastification extrusion, and appearance colorless is transparent, non-yellowing, and without poisonous and harmful substance in process.
Description
Technical field
The invention belongs to packaging film field, specially a kind of biodegrade PVA stretch wrap film and preparation method thereof.
Background technique
Due to polyvinyl alcohol (PVA) material have the characteristics that it is degradable, so both at home and abroad for using polyvinyl alcohol to prepare
Degradable biodegradable material has done more research, embodies environmentally protective, reduction " white pollution " bring harm, real
The characteristic of existing sustainable development.PVA film preparation method is substantially to be produced with solution casting method, also has melting to squeeze in recent years
Blowing out is referred to as wet process and dry method.Wet process technique process, energy consumption is high, and low output, equipment investment is big, and production produces
Quality is not easy to control.
Chinese patent CN107891560A, a kind of preparation method of water-soluble stretch film are to use a large amount of water to make plasticizer
The tape casting production, water-soluble express train are not able to satisfy the requirement of stretched film, and it is then molten to meet water, and form sticky shape pollution by Bao Pinbiao
Face, air humidity influence also very greatly, and excessive be also easily precipitated of small molecule plasticizers influences appearance.
Melting extrusion blowing is modified based on plasticizing, and plasticity, reprocessing film forming, since PVA is polyhydroxy base junction are prepared
Structure makes melting temperature close with decomposition temperature there are intermolecular with intramolecular strong hydrogen bonding active force, it is difficult to thermoplastic processing film forming,
Make that its complex process, technical difficulty during dry process are big, energy consumption is high.
Summary of the invention
The present invention is the deficiency in order to solve to make it be difficult to form a film due to the polyhydroxy structure of PVA in the prior art, and
A kind of biodegrade PVA stretch wrap film and preparation method thereof is provided.
One of the objects of the present invention is to provide a kind of biodegradable PVA nontoxic and pollution-free, at low cost to stretch winding
Film；The second object of the present invention is to provide a kind of method for preparing biodegradable PVA stretch wrap film.
The technical solution adopted by the present invention to solve the technical problems is:
The tensile strength of a kind of biodegrade PVA stretch wrap film, the stretch wrap film is greater than 30MPa, and elongation is big
In 150%, the stretch wrap film is prepared by the raw material of following parts by weight:
The modifying agent is by gathering own propyl ester A, cumyl peroxide B, at least one water
Soluble pyrophosphates C and at least one inorganic acid D are combined.
Preferably, PVA selects the PVA particle of the degree of polymerization 500~2600, the alcoholysis degree of PVA particle is 80~100%,
PVA particle including partial alcoholysis and complete alcoholysis, 60 mesh of grain diameter~120 mesh.
Preferably, the water-soluble sodium salt is at least one in sodium pyrophosphate, Sodium Acid Pyrophosphate and potassium pyrophosphate
Kind, inorganic acid is dilute sulfuric acid or phosphoric acid, and the mass ratio of component A, B, C and D are 3: 1: 2: 1.
Polycaprolactone has good biocompatibility, good organic polymer compatibility and good biodegrade
Property, cumyl peroxide promotes polycaprolactone and PVA to realize high stability crosslinking, increases the flexibility of film forming raw material, pyrophosphoric acid
Saline solution is in alkalescent, and inorganic acid-conditioning solution is weakly acidic, under mildly acidic conditions, is with polycaprolactone and pyrophosphate
Main component, while being added and generating synergistic effect for the modified different phenylpropyl alcohol of peroxidating two, high molecular weight reactive occurs, reduces PVA
Regularity, reduce fusing point, thus solve thermoplastic processing film forming technical problem.
Preferably, the plasticizer is glycerine, propylene glycol, polyethylene glycol, an acetoglyceride, two triacetins
At least two in ester, triacetyl glycerine, 1,4-butanediol and glycerol.
Preferably, the processing aid is by mass ratio (0.5~1.1): 1.1: (0.3~3): the lubricant of (0~2),
Antioxidant and bleeding agent composition,
The lubricant be selected from zinc stearate, calcium stearate, magnesium stearate, barium stearate, oleamide, erucyl amide,
At least two in stearic amide and methyl methacrylate；
The antioxidant is selected from antioxidant 1010, antioxidant 264, antioxidant 1076, irgasfos 168, antioxidant 2246, resists
At least two in oxygen agent 1135, antioxidant 300 and antioxidant 330；
The bleeding agent selects lauramide hydroxy sulfo lycine, coconut oleoyl amine hydroxy sulfo lycine and polyoxyethylene 12
At least one of alkyl ether.It is very effective to improve PVA biological degradability present invention introduces bleeding agent, overcome compost to drop
The secondary polycondensation of PVA influences disintegration rate in solution preocess；
The reinforcing agent selects at least one of nano silica, nano-titanium dioxide, talcum powder and magnesium hydroxide.
A kind of preparation method of biodegrade PVA stretch wrap film, the method comprises the following steps:
S1, PVA are granule modified
The modifying agent of the PVA particle of formula ratio and formula ratio is uniformly mixed, in 40~60 DEG C of constant temperature stirring 15~
20min；
S2, pre- plasticising processing
Plasticizer, deionized water and the processing aid of formula ratio are added in the material of step S1, heats while stirring 45
25~45min of plasticising processing at~120 DEG C；
S3, granulation
Will pre- plasticising treated that mixture is placed in single screw extrusion machine or double screw extruder, temperature control 100
~220 DEG C, extruding pelletization；
S4, blown film
The particle of step S3 is squeezed out or tubular film base formed after injection molding, while hot or is heated to melt flows state,
High pressure gas is passed through by periosteum inflation to certain thickness, up to biodegrade PVA stretch wrap film after cooling and shaping.
The beneficial effects of the present invention are:
(1) present invention process is simple, cost is relatively low, is conducive to promote, without poisonous and harmful substance, the present invention in process
The tensile strength of the stretch wrap film of preparation is greater than 30MPa, and elongation is greater than 150%, and normal-temperature water is insoluble, and physical property is excellent
It is different；
(2) present invention introduces bleeding agents, very effective to improve PVA biological degradability, overcome in compost degradation process
The secondary polycondensation of PVA influences disintegration rate；
(3) the modified PVA plasticized systems of the present invention can realize 0.5-10g/10min.190 DEG C of .2160g- of melt index
5000g, 100 DEG C -220 DEG C of processing temperature, processing fluidity is excellent, is advantageously implemented fusion plastification extrusion.
Specific embodiment
Below by embodiment, explanation is further described to technical solution of the present invention.
Embodiment 1:
A kind of biodegrade PVA stretches the preparation method of winding A/B double-layer structure film:
A film the preparation method is as follows:
S1,85 parts of PVA (0588/1788=3/7) are uniformly mixed with 10 parts of modifying agent, modifying agent is mass ratio 3: 1: 2:
1 polycaprolactone, cumyl peroxide, sodium pyrophosphate and phosphoric acid stirs uniformly mixed material in 40~60 DEG C of constant temperature
20min；
S2, step S1 material in be added 15 parts of glycerol, 15 parts of polyethylene glycol 400,5 parts of deionized water, antioxidant 1010
0.6 part, 0.5 part of antioxidant 300,0.45 part of zinc stearate, 3 parts of lauramide hydroxy sulfo lycine put into high mixer and increase in advance
Modeling processing, heat while stirring the plasticising processing 40min at 45~120 DEG C；
S3, by pre- plasticising treated mixture 100~220 DEG C at a temperature of extruding pelletization to get component A；
B film the preparation method is as follows:
S4,85 parts of PVA (0599/1799=3/7) are uniformly mixed with 10 parts of modifying agent, modifying agent is mass ratio 3: 1: 2:
1 polycaprolactone, cumyl peroxide, sodium pyrophosphate and phosphoric acid stirs uniformly mixed material in 40~60 DEG C of constant temperature
20min；
S5, step S1 material in be added 20 parts of glycerol, 1 part of polyethylene glycol 400,6 parts of deionized water, antioxidant 1010
0.6 part, 0.5 part of antioxidant 300,0.6 part of zinc stearate, 0.5 part of methyl methacrylate, coconut oleoyl amine hydroxy sulfo lycine
2.5 parts, 0.2 part of nano silica, 0.2 part of talcum powder, 1.5 parts of titanium dioxide put into plasticising processing in advance, Bian Jia in high mixer
Hot side stirring plasticising processing 40min at 45~120 DEG C；
S6, by pre- plasticising treated mixture 100~220 DEG C at a temperature of extruding pelletization to get B component；
S7, blowfilm shaping in the inflation film manufacturing machine of component A and B component investment A/B double membrane structure is stretched into winding to get PVA
Film.
The tensile strength of the PVA stretch wrap film of the embodiment of the present application preparation is 45MPa, elongation 166%.
Embodiment 2:
A kind of biodegrade PVA stretches the preparation method of winding A/B double-layer structure film:
A film the preparation method is as follows:
S1,70 parts of PVA (0588/2488=3/7) are uniformly mixed with 8 parts of modifying agent, modifying agent is mass ratio 3: 1: 2: 1
Polycaprolactone, cumyl peroxide, Sodium Acid Pyrophosphate and phosphoric acid, by uniformly mixed material in 40~60 DEG C of constant temperature
Stir 20min；
S2, step S1 material in be added 20 parts of glycerol, 1 part of polyethylene glycol 400,6 parts of deionized water, antioxidant 1010
0.6 part, 0.5 part of antioxidant 300,0.5 part of zinc stearate, 3 parts of coconut oleoyl amine hydroxy sulfo lycine put into high mixer and increase in advance
Modeling processing, heat while stirring the plasticising processing 40min at 45~120 DEG C；
S3, by pre- plasticising treated mixture 100~220 DEG C at a temperature of extruding pelletization to get component A；
B film the preparation method is as follows:
S4,70 parts of PVA (0599/2099=3/7) are uniformly mixed with 8 parts of modifying agent, modifying agent is mass ratio 3: 1: 2: 1
Polycaprolactone, cumyl peroxide, Sodium Acid Pyrophosphate and phosphoric acid, by uniformly mixed material in 40~60 DEG C of constant temperature
Stir 20min；
S5, step S1 material in be added 20 parts of glycerol, 1 part of polyethylene glycol 400,6 parts of deionized water, antioxidant 1010
0.6 part, 0.5 part of antioxidant 300,0.6 part of zinc stearate, 0.5 part of methyl methacrylate, polyoxyethylene lauryl ether
0.35 part, 0.3 part of nano silica, 0.6 part of nano-titanium dioxide put into plasticising processing in advance in high mixer, compile heating side and stir
Mix the plasticising processing 40min at 45~120 DEG C；
S6, by pre- plasticising treated mixture 100~220 DEG C at a temperature of extruding pelletization to get B component；
S7, blowfilm shaping in the inflation film manufacturing machine of component A and B component investment A/B double membrane structure is stretched into winding to get PVA
Film.
The tensile strength of the PVA stretch wrap film of the embodiment of the present application preparation is 43MPa, elongation 163%.
Embodiment described above is preferred version of the invention, is not intended to limit the present invention in any form,
There are also other variants and remodeling on the premise of not exceeding the technical scheme recorded in the claims.
Claims (6)
1. a kind of biodegrade PVA stretch wrap film, which is characterized in that the stretch wrap film by following parts by weight raw material system
It is standby to form:
Benzene B, at least one water solubility pyrophosphate C and at least one inorganic acid D are combined.
2. biodegrade PVA stretch wrap film according to claim 1, which is characterized in that the PVA selection degree of polymerization 500~
2600 PVA particle, the alcoholysis degree of PVA particle are 80~100%, the PVA particle including partial alcoholysis and complete alcoholysis, particle
60 mesh of partial size~120 mesh.
3. biodegrade PVA stretch wrap film according to claim 1, which is characterized in that the water solubility pyrophosphate
For at least one of sodium pyrophosphate, Sodium Acid Pyrophosphate and potassium pyrophosphate, inorganic acid is dilute sulfuric acid or phosphoric acid, component A, B,
The mass ratio of C and D is 3: 1: 2: 1.
4. biodegrade PVA stretch wrap film according to claim 1, which is characterized in that the plasticizer be glycerine,
In propylene glycol, polyethylene glycol, an acetoglyceride, two acetoglycerides, triacetyl glycerine, 1,4-butanediol and glycerol extremely
It is two kinds few.
5. biodegrade PVA stretch wrap film according to claim 1, which is characterized in that the processing aid is by quality
Than (0.5~1.1): 1.1: (0.3~3): lubricant, antioxidant, bleeding agent and the reinforcing agent composition of (0~2),
The lubricant is selected from zinc stearate, calcium stearate, magnesium stearate, barium stearate, oleamide, erucyl amide, tristearin
At least two in sour amide and methyl methacrylate；
The antioxidant is selected from antioxidant 1010, antioxidant 264, antioxidant 1076, irgasfos 168, antioxidant 2246, antioxidant
1135, at least two in antioxidant 300 and antioxidant 330；
The bleeding agent selects lauramide hydroxy sulfo lycine, coconut oleoyl amine hydroxy sulfo lycine and polyoxyethylene lauryl base
At least one of ether；
The reinforcing agent selects at least one of nano silica, nano-titanium dioxide, talcum powder and magnesium hydroxide.
6. the preparation method of biodegradable PVA stretch wrap film, feature described in a kind of Claims 1 to 5 any one exist
In, the method comprises the following steps:
S1, PVA are granule modified
The modifying agent of the PVA particle of formula ratio and formula ratio is uniformly mixed, stirs 15~20min in 40~60 DEG C of constant temperature；
S2, pre- plasticising processing
Plasticizer, deionized water and the processing aid of formula ratio are added in the material of step S1, heats while stirring 45~120
25~45min of plasticising processing at DEG C；
S3, granulation
Will pre- plasticising treated that mixture is placed in single screw extrusion machine or double screw extruder, temperature control 100~220
DEG C, extruding pelletization；
S4, blown film
By the particle of step S3 through extrusion or tubular film base formed after injection molding, while hot or it is heated to melt flows state, be passed through
High pressure gas is by periosteum inflation to certain thickness, up to biodegrade PVA stretch wrap film after cooling and shaping.
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| CN201910070484.XA CN109825016A (en) | 2019-01-24 | 2019-01-24 | A kind of biodegrade PVA stretch wrap film and preparation method thereof |
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| CN201910070484.XA CN109825016A (en) | 2019-01-24 | 2019-01-24 | A kind of biodegrade PVA stretch wrap film and preparation method thereof |
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Cited By (3)
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| CN111231362A (en) * | 2020-01-15 | 2020-06-05 | 江门市爱格环保材料有限公司 | Preparation process of water-soluble film |
| CN111978664A (en) * | 2020-07-16 | 2020-11-24 | 张家港市三企包装制品有限公司 | Preparation method of water-soluble winding film |
| CN114573893A (en) * | 2020-12-01 | 2022-06-03 | 中国石油天然气股份有限公司 | Middle layer composite material of heavy packaging film and preparation method thereof |
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Effective date of registration: 20210121 Address after: 255000 room 1103, unit 1, building 3, 77 Liuquan Road, Zhangdian District, Zibo City, Shandong Province Applicant after: Zhu Pengtao Address before: 236500 No. 797, Renmin East Road, Jieshou City, Fuyang City, Anhui Province Applicant before: ANHUI DINGYANG BIO-BASED MATERIALS Co.,Ltd. |
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