CN106519400A - Degradable polyolefin heat-shrinkable film material and preparation method thereof - Google Patents
Degradable polyolefin heat-shrinkable film material and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a degradable polyolefin heat-shrinkable film material which comprises polyolefins, a photoinitiator and a modified molecular sieve catalyst. The content of the modified molecular sieve catalyst in the film material is 0.1-5 wt%; the content of the photoinitiator is 1-10 wt%; and the modified zeolite catalyst is a zirconium/zinc-supported titanium oxide/ZSM-5 catalyst, wherein the supporting capacity of zirconium is 1-5 wt%, the supporting capacity of zinc is 0.5-3 wt%, and the mass ratio of the oxide to ZSM-5 is 1:(2-5). By using the polyolefin material as the main raw material, only small amounts of the photoinitiator and nano modified molecular sieve catalyst are needed, so the original mechanical and physical properties of the polyolefin material are not influenced. The polyolefin material can be slowly degraded in the natural environment to generate CO2 and water which can hardly influence the environment; and thus, the polyolefin material is environment-friendly.
Description
Technical field
The present invention relates to a kind of polyolefin film materials, the especially a kind of Degradable polyolefin membrane material of environmental protection and its preparation
Method.
Background technology
Process blow molding of the heat-shrinkable film (POF films) using hurried cooling and shaping, the production technology of this quenching
To be designed according to high polymer orientation principle, when resin by plasticizing is extruded into embryophoric membrane completely after, polymer in vitrification point and
Pressure stretching is carried out along two directions in length and breadth between glutinous stream temperature, the strand of polymer is orientated along draw direction, at this moment will be thin
The hurried cooling of film, by the strain " freezing " produced by stretching orientation.When film is reheated to " defrosting " temperature, will produce
Stress relaxation, that is, oriented strand generation disorientation, now, are forced in the drawing chain of tense situation, then recover
The folded chain of relaxed state to before orientation, therefore give shrink film good shrinkage.Especially in packaging industry, shrink film with
The characteristics of which is of high quality and at a reasonable price, is replacing other packaging material.
As the material of shrink film, there is following requirement：Longitudinal direction (MD) shrinkage factor is reduced as shrinking,
Increase laterally (TD) shrinkage factor.Because when transition is shunk in longitudinal direction (MD), film will produce likeness in form " smile " or " frowning " pleat
Wrinkle.Shrink film can run into the problem that storage is shunk in storage, and so shrink film will not reach preferably receipts when in use
Shrinkage, and cause shrink film disabler.Therefore, when shrink film resin is developed, storage environment is considered as, by resin shrinkage
Temperature design is more than storage environment.Shrink film can also be stored under cold environment, but require that resin cold resistance is good.Shrink
When film is used as packaging material, it is desirable to preferable toughness, larger tearing toughness.
At present, the main heat shrink films of China have PVC, PE, BOPP, POF etc., and these heat shrink films materials are extensive
Be applied to our life, but due to China's Waste sorting recycle system it is also unsound, a considerable amount of heat shrink films materials
Without effective recycling, but it is directly entered in rubbish.As these membrane materials are all to adopt high molecular polymer, in nature
Under the conditions of be difficult to decompose, therefore be easy to produce " white pollution ", the self degradation ability for improving these materials be change this
One of effective way of present situation.
CN103059325 A disclose a kind of novel starch base cellulose Degradable plastic film, accurate by following quality proportioning
Standby raw material：20～30 parts of starch；15～20 parts of polyvinyl alcohol；10～20 parts of cotton fiber；5～10 parts of glacial acetic acid；Acetic anhydride 5～10
Part；0.1～0.5 part of catalyst；2～5 parts of crosslinking agent；3～6 parts of glycerine；2～5 parts of glyoxal；By cotton fiber add glacial acetic acid,
Acetic anhydride, while adding catalyst, 2h is reacted in 50 DEG C of waters bath with thermostatic control, obtains acetate fiber；Starch Polyvinyl alcohol, glycerine and second two
Aldehyde high-speed stirred at 90 DEG C, reacts 1h, obtains starch solution；Acetate fiber and starch solution are mixed, crosslinking agent is added,
High-speed stirred 2h at 70 DEG C, casting film-forming take off film after 80 DEG C of drying 3h.Obtained Degradable plastic film good mechanical performance, drop
Solution speed is fast；Degradation plastic membrane preparation method is simple, it is easy to operate.
CN103160012 A disclose a kind of oxygen barrier and degredation plastic film, and its raw material components and weight are respectively：
100 parts of low density polyethylene (LDPE)；50～70 parts of PBM masterbatch；20～40 parts of pulullan polysaccharide；2～4 parts of antioxidant；Ultraviolet is inhaled
Receive 0.5～1 part of agent.The film has preferable mechanical property and degradability.But there is a problem of that price is higher.
At present to be all that the material to biomass source carries out secondary operation modified for existing degradable membrane material great majority, this
Although a little membrane materials have good degradability, mechanical performance and processing characteristics are poor, and price is higher, it is difficult to promote
Use.
The content of the invention
The main composition of heat shrink films is polyolefin, and polyolefin under natural environment is difficult to degrade, and China is current
Garbage reclamation is processed by the way of landfill or air storage using imperfection, a big chunk rubbish is gone back, substantial amounts of thermal contraction
Membrane material can be entered in house refuse, be difficult to be decomposed under stacking or landfill state naturally, so as to form so-called " white dirt
Dye ", therefore develop and have broad prospects with the heat shrink films of degradation function.Current degradable heat shrink films material is most
Made using the organic high molecular polymer such as material such as modified starch, cellulose, shitosan of biomass, but these materials have
Have mechanical performance not good, price costly, the complicated shortcoming of processing technology.The present invention provides one kind with polyolefin as basic material
Material, by the method for adding modified zeolite catalyst improve heat shrink films at normal temperatures under illumination condition from degradation speed, from
And solve " white pollution " problem in life.The present inventor is found surprisingly that, modified zirconia is added in polyolefine material
Zeolite-titanium oxide catalyst, can improve polyolefin decomposition rate at normal temperatures, interrupt the carbochain of polymer, by polyolefin
Material can be decomposed into low molecular hydro carbons and carbon dioxide, water, and these materials further can be absorbed in natural environment
Decomposition and inversion, so as to reach the purpose of environmental protection.
The present invention discloses a kind of Degradable polyolefin heat shrink films material, and the membrane material includes polyolefin, light trigger
And modified molecular sieve catalyst；Content of the modified molecular sieve catalyst in membrane material is 0.1-5wt%, preferably 0.5-
1wt%；The content of the light trigger is 1-10wt%, more preferably 3-5wt%；The modified zeolite catalyst be load zirconium and
The titanium oxide of zinc/ZSM-5 catalyst, the load capacity of wherein zirconium is 1-5wt%, and the load capacity of zinc is 0.5-3wt%, titanium oxide and
The mass ratio of ZSM-5 is 1:2-5.
The particle diameter of the modified molecular screen is 10-200nm, more preferably 50-100nm；The light trigger is styrax
One kind in class, benzophenone class, benzoic acid alkyl base ester, anthrone.
The polyolefin is polyethylene, one or more in polypropylene, polyvinyl chloride.
The preparation method of the modified molecular sieve catalyst, comprises the following steps, and silicon source, silicon source, titanium source and template are just
Butylamine is according to mol ratio 30-60:1:0.2-2:1-10 is mixed, and is aged at 24-48h, 200-300 DEG C brilliant at 120-160 DEG C
Change 12-24h and obtain molecular screen primary powder, molecular screen primary powder calcines 1-10h at 500-800 DEG C, obtains titanium modified ZSM-5 molecule
Sieve；Titanium modified zsm-5 zeolite impregnates 12-36h in the saturated aqueous solution of zinc and zirconium, is calcined after being dried at 200-350 DEG C
1-5h obtains final product the modified molecular sieve catalyst.
The silicon source is waterglass, orthosilicic acid, the one kind in metasilicic acid, and source of aluminium is aluminum sulfate, sodium metaaluminate, nitric acid
One kind in aluminium；The titanium source is tetrabutyl titanate, the one kind in tetraethyl titanate.
Surfactant can also be included in the raw material, the surfactant is alkylbenzenesulfonate, polyethylene glycol
In one kind, more preferably neopelex.
A kind of preparation method of Degradable polyolefin heat shrink films material, comprises the following steps：By polyolefin, light-initiated
Agent, modified molecular sieve catalyst and other additives are sufficiently mixed；Feed the mixture into extruder and melt extruding pelletization；General
Blown Film in grain addition inflation film manufacturing machine.
The extrusion temperature is 150-200 DEG C, preferably 160-170 DEG C；The temperature of Blown Film is 170-175 DEG C
Described other additives include the typical additives such as coupling agent, plasticizer, stabilizer.
The present invention's has the technical effect that：
1. the present invention is with polyolefine material as primary raw material, it is only necessary to add a small amount of light trigger and nano level modified molecular sieve
Catalyst, has substantially no effect on the original machinery of polyolefine material and physical property.
2. the polyolefine material in the present invention can slowly occur degraded under natural environment, and generation does not almost have to environment
The CO of impact2And water, it is very friendly for environment.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention
Limit the present invention.
Embodiment 1：
The preparation of modified molecular sieve catalyst：
Waterglass, aluminum sulfate, tetrabutyl titanate and template n-butylamine are according to mol ratio 30:1:0.2:1 mixes, 120 DEG C
Lower ageing 24h, at 200 DEG C, crystallization 24h obtains molecular screen primary powder, and molecular screen primary powder calcines 8h at 550 DEG C, obtains titanium and is modified
ZSM-5 molecular sieve；Titanium modified zsm-5 zeolite impregnates 24h in the saturated aqueous solution of zinc and zirconium, is forged after being dried at 200 DEG C
Burn 5h and obtain final product the modified molecular sieve catalyst.
The preparation of heat shrink films material：
Will be low density polyethylene (LDPE), two propiophenone of light trigger, modified molecular sieve catalyst, coupling agent, plasticizer, stabilizer abundant
Mixing；Feed the mixture into extruder and melt extruding pelletization；Particle is added into Blown Film in inflation film manufacturing machine.
Embodiment 2：
The preparation of modified molecular sieve catalyst：
Waterglass, aluminum sulfate, tetrabutyl titanate and template n-butylamine are according to mol ratio 60:1:2:2 mix, at 150 DEG C
Ageing 24h, at 300 DEG C, crystallization 12h obtains molecular screen primary powder, and molecular screen primary powder calcines 1h at 7000 DEG C, obtains titanium and is modified
ZSM-5 molecular sieve；Titanium modified zsm-5 zeolite impregnates 12h in the saturated aqueous solution of zinc and zirconium, is forged after being dried at 3500 DEG C
Burn 1h and obtain final product the modified molecular sieve catalyst.
The preparation of heat shrink films material：
Will be low density polyethylene (LDPE), two propiophenone of light trigger, modified molecular sieve catalyst, coupling agent, plasticizer, stabilizer abundant
Mixing；Feed the mixture into extruder and melt extruding pelletization；Particle is added into Blown Film in inflation film manufacturing machine.
Comparative example 1（Common polyolefin film）：
Low density polyethylene (LDPE), coupling agent, plasticizer, stabilizer are sufficiently mixed；Feed the mixture into extruder thawing extrusion to make
Grain；Particle is added into Blown Film in inflation film manufacturing machine.
Quantitative measurement and the decomposition experiment under illumination condition, the decomposition reality are carried out respectively to embodiment and comparative example
Test room to refer under the illumination of natural environment and normal temperature and pressure conditionses, laboratory sample is placed after a period of time by calculating matter of weighing
The mode of quantitative change rate checks its degraded situation.Concrete data are as follows：
| Decomposition experiment（6 months） | Elongation rate of tensile failure（%） | Tearing strength（MPa） | Heat distortion temperature（℃） | |
| Embodiment 1 | 88.6% | 381 | 29 | 165 |
| Embodiment 2 | 87.3% | 373 | 28 | 164 |
| Comparative example 1 | 99.8% | 402 | 30 | 156 |
From correction data it is seen that, the physical property of Degradable polyolefin heat shrink films material of the present invention changes very
It is little, and Degradable polyolefin material of the present invention there occurs significant degraded under field conditions (factors), this explanation light trigger two
Propiophenone and modified molecular sieve catalyst there occurs synergy, and polyolefine material occurs significantly drop in the presence of catalyst
Solution, achieves unexpected technique effect.
Claims (9)
1. a kind of Degradable polyolefin heat shrink films material, the membrane material include polyolefin, light trigger and modified molecular screen
Catalyst；Content of the modified molecular sieve catalyst in membrane material is 0.1-5wt%, preferably 0.5-1wt%；The light draws
The content for sending out agent is 1-10wt%, more preferably 3-5wt%；The modified zeolite catalyst be load the titanium oxide of zirconium and zinc/
The load capacity of ZSM-5 catalyst, wherein zirconium is 1-5wt%, and the load capacity of zinc is the mass ratio of 0.5-3wt%, titanium oxide and ZSM-5
For 1:2-5.
2. membrane material as claimed in claim 1, it is characterised in that the particle diameter of the modified molecular screen is 10-200nm, more preferably
It is 50-100nm；The light trigger is styrax class, benzophenone class, benzoic acid alkyl base ester, the one kind in anthrone.
3. membrane material as claimed in claim 1, it is characterised in that the polyolefin is polyethylene, in polypropylene, polyvinyl chloride
One or more.
4. membrane material as claimed in claim 1, it is characterised in that the preparation method of the modified molecular sieve catalyst, including with
Lower step, silicon source, silicon source, titanium source and template n-butylamine are according to mol ratio 30-60:1:0.2-2:1-10 is mixed, 120-
Crystallization 12-24h at 24-48h, 200-300 DEG C is aged at 160 DEG C and obtains molecular screen primary powder, molecular screen primary powder is at 500-800 DEG C
Calcining 1-10h, obtains titanium modified zsm-5 zeolite；Titanium modified zsm-5 zeolite is impregnated in the saturated aqueous solution of zinc and zirconium
12-36h, at 200-350 DEG C calcines 1-5h after being dried and obtains final product the modified molecular sieve catalyst.
5. membrane material as claimed in claim 1, it is characterised in that the silicon source is waterglass, orthosilicic acid, in metasilicic acid
Kind, source of aluminium is aluminum sulfate, sodium metaaluminate, the one kind in aluminum nitrate.
6. membrane material as claimed in claim 1, it is characterised in that surfactant, the table can also be included in the raw material
Face activating agent is alkylbenzenesulfonate, the one kind in polyethylene glycol, more preferably neopelex.
7. as described in any one of claim 1-6 membrane material preparation method, comprise the following steps：By polyolefin, light trigger,
Modified molecular sieve catalyst and other additives are sufficiently mixed；Feed the mixture into extruder and melt extruding pelletization；By particle
Add Blown Film in inflation film manufacturing machine.
8. method as claimed in claim 7, it is characterised in that the extrusion temperature is 150-200 DEG C, preferably 160-170
℃；The temperature of Blown Film is 170-175 DEG C.
9. method as claimed in claim 7, it is characterised in that described other additives include coupling agent, plasticizer, stabilizer.
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| WO2018072746A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition, preparation method therefor and application thereof |
| CN109294189A (en) * | 2018-09-20 | 2019-02-01 | 张芸 | A kind of preparation method of high transparency heat shrinkable printing film |
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| WO2018072746A1 (en) | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition, preparation method therefor and application thereof |
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| CN109294189A (en) * | 2018-09-20 | 2019-02-01 | 张芸 | A kind of preparation method of high transparency heat shrinkable printing film |
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