CN106947179A - A kind of degradative plastic film for filler of being degraded containing string - Google Patents
A kind of degradative plastic film for filler of being degraded containing string Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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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
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The invention belongs to ground cover film manufacturing technology field, and in particular to a kind of degradative plastic film for filler of being degraded containing string.The degradative plastic film includes being used as the resin of ground membrane matrix, the degradable master batch for promoting Plastic-film disintegration, the degraded filler containing natural plant fibre powder, antifoggant, auxiliary agent.The resin as ground membrane matrix uses polyvinyl chloride（PVC）Or using by polyethylene（LDPE）, LLDPE（LLDPE）And metallocene PE（mPE）The hybrid resin that three kinds of resins are constituted.The plant cellulose such as powder of straw, powdered rice hulls, boll hull powder in the manufacture of the degradative plastic film, is microbial reproduction manufacturing condition in soil, and straw-returning is turned waste into wealth, and these natural strings play the role of to promote Plastic-film disintegration.
Description
Technical field
The present invention principally falls into ground cover film manufacturing technology field, and in particular to a kind of degraded filler containing string
Degradative plastic film.
Background technology
Covered ground film agricultural technology turns into the new cultivation technique that China grows up the seventies.Covered ground film
Agricultural technology is that thickness is close to ground surface covering for transparent and coloured (black, the white, green) mulch films of 0.01-0.02mm to be planted
Training, is a kind of most simple and easy to do protecting field form, and it is to improve the soil moisture, promote well developed root system, so as to improve work that it, which is acted on,
The yield and the output value of thing, in addition, covering with ground sheeting also has guarantor Moisture, water saving, weeding, promotion organic fertilizer to decompose and keep loosing soil
Useful effects such as (keeping soil from packing together).
Traditional mulch film used has intensity high, and light weight is anticorrosive, easy processing, the low feature of price.People's
It is used widely in production and living.But to bring and also bring serious negative effect while greatly convenience, by
Clay is stained with the discarded mulch film after, it is impossible to reclaim, soil property and crop cultivation can be influenceed by being placed in farmland, will be about
The century-old time could degrade.Extended residual can bring serious environmental pollution in natural environment, not only influence the ecological balance, together
When also threaten the health of the mankind, if the mulch film after use can not degrade, white pollution can be caused to soil by remaining in soil.
Optically and biologically degrading mulch film is out of doors in the presence of the weather conditions such as ultraviolet, temperature, humidity, cause from outward appearance to
Inherent quality changes, such as：Under mechanical property, tensile strength, the obvious reduction of elongation at break and angle tear strength, molecular weight
Drop, outward appearance change fragmentates, efflorescence.Newborn oxy radical by representative of carbonyl, carbon source can be provided for microorganism and continues to be given birth to
Thing is degraded.But in the prior art, often use, wood administration's starch and chitin degradative plastic film are filled out in the preparation of degradative plastic film
Degradation agent is filled, due to each kind of starch [C6H7O2‐(OH)2] contain great amount of hydroxy group (- OH) and polyethylene kind Polymers Phase capacitive in n
Difference, easily absorbs water, therefore in TPO difficulties in dispersion, it is necessary to coupling agent etc. need to be added to starch conversion processing, not only technique is cumbersome,
High cost and effect is undesirable, transparency reduction.Therefore, rest on for many years in the puzzlement that can not implement and promote.
Therefore, it is a kind of without using degradative plastic film of the starchy material as mulch film inserts to need exploitation badly.
The content of the invention
In order to solve the above problems, the present invention provides a kind of degradative plastic film for filler of being degraded containing string.In the drop
Contain biodegradation agent and photodegradable aid in the degradable master batch added in the manufacture for solving mulch film, with dual degraded effect, be
Accelerate biodegradation rate, the plant celluloses such as powder of straw, powdered rice hulls, boll hull powder are added in mulch film manufacturing process, are soil
Middle microbial reproduction manufacturing condition, straw-returning is turned waste into wealth, and these natural strings play the role of to promote Plastic-film disintegration.
The present invention is achieved by the following technical solutions：
It is a kind of containing string degrade filler degradative plastic film, the degradative plastic film include as membrane matrix resin,
For promoting the degradable master batch of Plastic-film disintegration, the degraded filler containing natural plant fibre powder, antifoggant, auxiliary agent.
Further, the resin as ground membrane matrix is using polyvinyl chloride (PVC) or using by polyethylene
(LDPE), the hybrid resin that three kinds of resins of LLDPE (LLDPE) and metallocene PE (mPE) are constituted, according to
The species of the resin as ground membrane matrix determines the addition species of the auxiliary agent.
Further, the preparing raw material of the degraded filler includes degraded filler resin, natural plant fibre powder, coupling
Agent, dispersant and lubricant；Wherein described natural plant fibre powder is used in powdered rice hulls, powder of straw, peanut shell powder and boll hull powder
Any one or it is two or more；The particle diameter of the natural plant fibre powder is controlled to be more than 800 mesh, moisture≤3%.The stalk
Powder is corn, water paddy and wheat, cotton, the powder of potatoes and other crops stalk.
Further, when it is described as mulch film matrix resin use polyvinyl chloride (PVC) when, the auxiliary agent include plasticizer
With PVC compound stabilizers, the plasticizer is dioctyl adipate (DOA), o-phthalic acid dibutyl ester (DOP), O-phthalic
Any one or any two or more combinations in sour dibutylester (DBP) and epoxidized soybean oil；The PVC compound stabilizers are
Calcium-zinc composite stabilizing agent；
Further, the degradable master batch includes polyvinyl chloride (PVC), biodegradation agent, photodegradable aid, dispersant；Institute
Stating biodegradation agent includes polycaprolactone (PCL), poly-succinic fourth diester (PBS) and ATBC (TBC), the light drop
Solution agent is ferric stearate, and the dispersant is double ethylene stearmides (EBS)；
According to weight ratio meter, the shared parts by weight of each component are in the degradable master batch：50 parts of polyvinyl chloride (PVC),
15-17 parts of polycaprolactone (PCL), 30-35 parts of poly-succinic fourth diester (PBS), 1.5-1.8 parts of ferric stearate, the fourth of citric acid three
0.6-0.8 parts of ester (TBC), 0.5-0.6 parts of double ethylene stearmides (EBS).
The degraded filler includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant and lubricant；
Wherein, the degraded filler uses polyvinyl chloride (PVC) with resin, and the natural plant fibre powder uses powdered rice hulls and powder of straw
In one or two, the coupling agent uses silane coupler, and the dispersant uses ethylene bis stearamide (EBS), institute
State lubricant and use HSt.
According to weight ratio meter, parts by weight shared by each component are in the degradable master batch：Degraded filler resin 25 part, day
Right 1-1.5 parts of 15-18 parts of plant fiber powder, 0.4-0.6 parts of coupling agent, 0.5-0.7 parts of dispersant and lubricant；
Further, the degradative plastic film also includes impact modifier and toner, wherein the impact modifier uses MBS
Resin；
By weight, parts by weight shared by each component are in the degradative plastic film：100 parts of polyvinyl chloride (PVC), MBS trees
6-10 parts of fat, 5-6 parts of dioctyl adipate (DOA), 15-17 parts of o-phthalic acid dibutyl ester (DOP), dibutyl phthalate (DBP)
(DBP) 13-16 parts, 5-7 parts of epoxidized soybean oil, 2-2.5 parts of calcium-zinc composite stabilizing agent, 18-24 parts of degradable master batch, degraded filler
20-26 parts, antifoggant, 0.8-1.2 parts, 1-2 parts of toner.
Further, when the resin as ground membrane matrix uses the hybrid resin, the auxiliary agent is scattered profit
Lubrication prescription；
The degradable master batch includes polyethylene (LDPE), biodegradation agent, photodegradable aid, biodegradation material, bulking agent；
The biodegradation agent is the polyester of polyester branches derivative and polyadipate-terephthalic acid (TPA)-butanediol-terpolymer
(PBAT)；The photodegradable aid is ferric stearate；The bulking agent is the fourth fat (TBT) of metatitanic acid four
By weight, parts by weight shared by each component are in the degradable master batch：50 parts of polyethylene (LDPE), polyester branch
38-40 parts of chain derivative, polyadipate -15-17 parts of the polyester (PBAT) of terephthalic acid (TPA)-butanediol-terpolymer, metatitanic acid
Four 0.5-0.6 parts of fourth fat (TBT), 1.2-1.5 parts of ferric stearate.
Further, the preparing raw material of the degraded filler includes degraded filler resin, natural plant fibre powder, coupling
Agent, dispersant and lubricant；According to weight ratio meter, the shared parts by weight of each component are：30 parts of resin of degraded filler, natural plant
1-1.2 parts of 18-20 parts of fibres powder, 0.3-0.5 parts of coupling agent, 0.8-1 parts of dispersant and lubricant；
Wherein, the degraded filler with resin mixing using polyethylene (LDPE) and LLDPE (LLDPE)
The quality of the hybrid resin of polyethylene (LDPE) and LLDPE (LLDPE) in resin, and the hybrid resin
Than for 1:1；The natural plant fibre powder uses the one or two in powdered rice hulls and powder of straw；The coupling agent uses silane
Coupling agent, the dispersant uses zinc stearate, and the lubricant uses Tissuemat E (PE waxes)；
Further, by weight, parts by weight shared by each component are in the degradative plastic film：Polyethylene (LDPE) 25
Part, 20 parts of LLDPE (LLDPE), 5 parts of metallocene PE (mPE), 10-20 parts of degradable master batch, degraded filler
25-40 parts, 0.5-1 parts of antifoggant, 1-2 parts of double ethylene stearmides (EBS).
The Advantageous Effects of the present invention：
Added with string shell powder in the formula of degradative plastic film of the present invention, string shell powder is derived from powdered rice hulls or straw
Stalk powder, it is to avoid above-mentioned agricultural wastes burn or buried pollution on the environment；Meanwhile, substituted using string shell powder
The technological deficiency of starch fillers of the prior art.
Degradative plastic film of the present invention can be realized and the degradative plastic film is degraded by controlling the addition of degradable master batch
The control of time.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments to the present invention
It is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not used to
Limit the present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiied
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Embodiment 1
The macromolecular material of manufacture mulch film has high density polyethylene (HDPE) (LDPE), LLDPE (LLDPE), second
Alkene-acetate ethylene copolymer (EVA), polyvinyl chloride (PVC) etc. are a variety of.In the present embodiment, prepared using polyvinyl chloride (PVC)
Degradative plastic film, the mulch film based on PVC has softness, the high grade of transparency, a gas permeability (O2, CO2), heat insulating ability is suitable, antifog, dust-proof,
The advantages of comfortable feel and extension appropriateness.Meanwhile, polyvinyl chloride resin is macromolecular material most degradable in many high polymers, is selected
Suspension method GS-3 type resins, GS-3 types resin be white powder, molecular weight it is suitably good with plasticizer stabilizer intermiscibility, while former
It is 75-250um to expect abundance, the low particle diameter of price, in multilayered structure model.
Add after photodegradable aid, then a series of complicated photooxidation can occur for ultraviolet light and the lower PVC macromoleculars of oxygen participation
Reaction：
P˙+O2→POO˙
P-H ˙ (excitation state)+O2 → POOH
POOH→POO˙+H
PO˙+HO˙
These free radicals continue to make by chain reaction under the conditionings such as natural conditions light, temperature, humidity, biological bacteria
With going down, cause PVC macromolecules degradations.When the energy of light wave is more than PVC macromolecular bond energys, chemical chain fracture, PVC will break
Split and become small molecule.Under being acted in light-ecological film, used mulch film is promoted to degrade on time, the choosing of plastics variety
With, it is necessary to it is engaged with degraded effect, this chemical bond rupture causes PVC to degrade.C-CL bond energys 326.6KJ/mol is poly- in PVC
What bond energy was minimum in compound consolidates most degradable.
It is a kind of containing string degrade filler degradative plastic film, the degradative plastic film include as membrane matrix resin,
For promoting the degradable master batch of Plastic-film disintegration, the degraded filler containing natural plant fibre powder, antifoggant, auxiliary agent.
The resin as ground membrane matrix uses polyvinyl chloride (PVC), according to the resin as ground membrane matrix
Species determines that the auxiliary agent includes plasticizer and PVC compound stabilizers.The plasticizer is dioctyl adipate (DOA), adjacent benzene
It is any one or any two or more in dioctyl phthalate dibutyl ester (DOP), dibutyl phthalate (DBP) (DBP) and epoxidized soybean oil
Combination；The PVC compound stabilizers are calcium-zinc composite stabilizing agent；
The preparing raw material of the degraded filler includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant
And lubricant；Wherein described natural plant fibre powder uses the one or two in powdered rice hulls and powder of straw；Control is described natural
The particle diameter of plant fiber powder is more than 800 mesh, moisture≤3%.The powder of straw is that corn, water paddy and wheat, cotton, potato etc. make
The powder of thing stalk.For many years, using starch for degradation agent plastic degradation technology more, great amount of hydroxy group is contained in starch, is easily inhaled
Water and PVC, LDPE blending are poor, the difficulties in dispersion in resin, are easily condensed between the particle of starch, and the mulch film transparency made is poor,
The modification high cost of starch, complexity, cumbersome, the present embodiment replaces starch using natural plant fibre powder, and natural plants are fine
Dimension can promote mulch film controlled degradation after use.
The degradable master batch includes polyvinyl chloride (PVC), biodegradation agent, photodegradable aid, dispersant；The biodegradation
Agent includes polycaprolactone (PCL), poly-succinic fourth diester (PBS) and ATBC (TBC), and the photodegradable aid is tristearin
Sour iron, the dispersant is double ethylene stearmides (EBS)；The degradable master batch component and content are as shown in table 1.
The component and content of the degradable master batch of table 1
| Sequence number | Title | Unit | Consumption | Remarks |
| 1 | PVC | Kg | 50 | GS-3 types |
| 2 | PCL | Kg | 16.5 | Polycaprolactone |
| 3 | PBS | Kg | 32.5 | Poly-succinic fourth diester |
| 4 | Fest | Kg | 1.5‐1,8 | Ferric stearate |
| 5 | TBC | Kg | 0.6‐0.8 | ATBC |
| 6 | EBS | Kg | 0.5‐0.6 | Double ethylene stearmides |
The degraded filler includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant and lubricant；
Wherein, the degraded filler uses polyvinyl chloride (PVC) with resin, and the natural plant fibre powder uses powdered rice hulls and powder of straw
In one or two, the coupling agent uses silane coupler, and the dispersant uses ethylene bis stearamide (EBS), institute
State lubricant and use HSt.Wherein, natural plant fibre includes various shell powder, powder of straw.Main component is：Cellulose, hemicellulose
Element and lignin.They are that natural degradation material is introduced into ground film component, not only reduce cost, and can promote
Degradation function, solves white pollution.
After being crushed due to natural plant fibre (800 mesh), greatly, therefore surface tension and polarity differ with macromolecule PVC
Blending is difficult between the two, and the coupling agent that must add extraordinary selection is surface-treated, and can be interpenetrated and be made with melting extrusion
Grain；Silane coupler is added in the present embodiment.The component and content of the degraded filler are as shown in table 2.
The component and content of the degraded filler of table 2
It is described degraded filler preparation method be：
1. above-mentioned formula precise is pressed；
2. material is added in cold batch mixer in order, mixing speed 65r/Min is stirred 20 minutes；
3. cooling granulation in double screw extruder, water is used；110 DEG C of processing temperature, 120 DEG C, 140 DEG C, 150 DEG C, membrana oralis
145℃；
4. that degradable master batch is made is standby for cooling and dicing.
The degradative plastic film also includes impact modifier and toner, wherein the impact modifier uses MBS resins；MBS
The addition of resin, can promote the pliability of PVC mulch films；From the MBS resin (first for adding transparent toughness reinforcing under mulch film requirement of low temperature
Base methacrylate-butadiene-styrene), MBS resins are good with PVC intermiscibilities, it is possible to increase impact strength, do not influence transparent
Degree.It is contemplated that PVDC (vinylidene chloride), CPVC (chliorinated polyvinyl chloride) etc. as blending resin to improve the quality of mulch film.
And the addition of MBS resins needs to be controlled.
Weight shared by each component is as shown in table 3 in the degradative plastic film
Component and weight in degradative plastic film described in table 3
The degradative plastic film preparation method is：
1. formula metering, above-mentioned 1-7 is sequentially added into heated type high-speed kneading machine (or banbury), 50
Stirred 5-8 minutes at a temperature of DEG C -60 DEG C.
2. granular degradable master batch and stalk masterbatch are continuously added, is stirred 10 minutes at normal temperatures.
3. it is discharged into the vacuum feeding device of curtain coating production line, into casting machine by membrana oralis, cooling shaping, is made automatically
Mulch film.
Degradative plastic film described in the present embodiment is molded using the tape casting and prepared, and results in ultra-thin mulch film (0.01mm is thick),
And the degradative plastic film thickness is uniform, internal stress free, transparency is high, not static electrification, and not dust suction is phozy, rub resistance, and air penetrability is fitted
Preferably etc., especially adapt to the land cover pattern under various natural conditions.
In the present embodiment, by can be by controlling the addition of degradable master batch, and then the regulation and control to degradation time be realized,
It can be widely used at south China, the north, various temperature, the field crop such as soybean, corn, wheat, paddy rice, and can be common
Vegetables, the field such as nursery, the cultivation such as extraordinary pollution-free vegetable, fruit, field crop can be made into being incubated of unique function, black
Color, white, green, bicolor mulching film, weed removal mulch film, the kind such as insect-repelling mulching film., can by the time requirement of digging after harvest after use
Control degraded.Realize the PVC mulch films of comprehensive controllable degradation time (pressing area, temperature, crop), above-mentioned controlled degradation time
The formula of degradative plastic film be to be realized by theoretical foundation of the mechanism of degradation of PVC polymers.
There is abundant stalk resource in China, and stalk total amount can reach 1,000,000,000 tons within 2014, cause crop straw burning more and more fiery,
To ecological environment heavy damage, the present invention is in mulch film manufacturing technology, and the discarded string of addition does filler, not only reduces
Cost, while enhancing the degradation function of mulch film, straw-returning is turned waste into wealth, of far-reaching significance.
Controlled degradation PVC mulch films of the present invention achieve positive effect for field.Such as covering with ground sheeting, planting vegetable,
Cucumber, fresh kidney beans, tomato, eggplant, cauliflower, onion, obtain effect it is as follows：Improve 2-3 DEG C of ground temperature；Reflected light substantially increases 30-
100%；Keep soil moisture 1-2.5%；Keep loosing soil；Improve structural behaviour；Porosity increase by 10%；Accelerate organic matter
Decompose；Improve soil nutrient content.And for example that seedling, well-ventilated, moisture can be incubated is suitable, foster for the early covering with ground sheeting raised rice seedlings
Point abundance obtain emerge, the actual effect of well developed root system, disease and insect resistance, can increase production 1-2 into.
Degradative plastic film of the present invention has the advantages that energy-saving and emission-reduction, low-carbon environment-friendly, volume increase, favour energy, promotes China modern
Agricultural integrates with internationalization, has filled up the domestic blank of like product.
Embodiment 2
In natural environment, in the presence of the irradiation of natural light, oxygen and various microorganisms, make polyethylene
(LDPE), linear high-density polyethylene (LLDPE), macromolecular chain fragment into small molecule, occur in appearance the embrittlement of efflorescence fragment with
And mechanical property (tensile strength, elongation at break, angle tear strength) is remarkably decreased, in addition it is degradable for carbon dioxide and
Water and disappear, and white pollution is not resulted in soil, environment.For the application effect for making mulch film keep optimal.The present embodiment is adopted
With the master of high density polyethylene (HDPE) (LDPE) linear high density polyethylene (LLDPE) and metallocene PE (m-PE) three kinds of polyolefin
Resin formula, wherein
Polyethylene LDPE：Trade mark 2420MI=2, density d=0.921；
LLDPE (LLDPE):Trade mark 7042MI=1-2 density d=0.918；
Metallocene PE (m-pE)：It is the most important technical progress of the nineties polyolefin industry and the novelty developed
Thermoplasticity kind, is a significant innovation.Because it is most suitable for the polyethylene that polymerization catalyst is produced using metallocene (MAO)
Ultra-thin mulch film is fit to do, formula and processing characteristics simplify, and extrusion energy consumption is low, and good toughness is nontoxic, transparent, excellent performance.
The proportioning of above-mentioned three kinds of resins is preferably LDPE:LLDPE:MpE=50:40:10；The assembling process is stable,
Product winds smooth, internal stress free, and compatibility is good, appearance transparent, and physical and mechanical properties can meet the standard requirement of mulch film, simultaneously
Addible plant fiber powder is easily compatible, not stratified, and immaculate is non-wrinkled, easy uncoiling, no tape.
It is a kind of containing string degrade filler degradative plastic film, the degradative plastic film include as membrane matrix resin,
For promoting the degradable master batch of Plastic-film disintegration, the degraded filler containing natural plant fibre powder, antifoggant, auxiliary agent.The conduct
The resin of ground membrane matrix is used by polyethylene (LDPE), LLDPE (LLDPE) and metallocene PE (mPE) three
The hybrid resin that resin is constituted is planted, polyvinyl chloride (PVC) is helped according to being determined the species of the resin as ground membrane matrix
Agent is dispersed lubricant；
The degradable master batch includes polyethylene (LDPE), biodegradation agent, photodegradable aid, biodegradation material, bulking agent；
The biodegradation agent is the polyester of polyester branches derivative and polyadipate-terephthalic acid (TPA)-butanediol-terpolymer
(PBAT)；The photodegradable aid is ferric stearate；The bulking agent is the fourth fat (TBT) of metatitanic acid four；
Wherein polyester branches derivative is a kind of new bio degradation agent, in pelletized form, the MI=5-8 fusing points 160- through survey
It is 170 DEG C, hygroscopic, it need to be dried 5-6 hours at 80 DEG C before use.The biological depressant prescription good degrading effect.Based in degradable master batch
The selection of component, above-mentioned degradation agent has preferable compatibility and plasticity；Above-mentioned degradable master batch can make mulch film in controllable time
Interior quick embrittlement, a certain degree of forfeiture mechanical property of efflorescence fragmentation, to the pollution-free zero-emission such as cultivated land, water source, crops.
The degradable master batch component and content are as shown in table 4.
The component and content of the degradable master batch of table 4
The preparation method of the degradable master batch is：By above-mentioned formula metering, by the degradation agent TBT high-speed mixers of drying
Stirring 15 minutes；After well mixed, granulated with double screw extruder, 165-185 DEG C of temperature range, water-cooled is granulated, dried
Preserve.
The preparing raw material of the degraded filler includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant
And lubricant；Wherein, the degraded filler with resin mixing using polyethylene (LDPE) and LLDPE (LLDPE)
The quality of the hybrid resin of polyethylene (LDPE) and LLDPE (LLDPE) in resin, and the hybrid resin
Than for 1:1；The natural plant fibre powder uses the one or two in powdered rice hulls and powder of straw；The coupling agent uses silane
Coupling agent, the dispersant uses zinc stearate, and the lubricant uses Tissuemat E (PE waxes)；
China is the maximum producing country and country of consumption of paddy rice, and resource is enriched very much, and it is broken into thin sprills, filling ground
Had many good qualities in film than past starch degradation.Conventional multi-purpose corn starch, wood administration's starch and chitin do degradative plastic film
Degradation agent is filled, due to each kind of starch [C6H7O2‐(OH)2] compatible with polyethylene kind high polymer containing great amount of hydroxy group (- OH) in n
Property it is poor, easily absorb water, therefore in TPO difficulties in dispersion, technique is cumbersome, high cost and effect is undesirable, transparency reduction.Rice
The main component of shell powder is cellulose, lignin, hemicellulose, and the fine powder of grinding is loosely easy to for squeezing to make with LDPE meltings
LDPE is penetrated into by silane coupler in the space of fiber, forms good combination interface.And Control granularity 800 mesh with
On, make it good with Compatibility in Plastics, using favourable.
The degraded filler component and content are as shown in table 5.
The degraded filler component of table 5 and content
It is described degraded filler preparation method be：
1) formula is pressed by each material precise；
2) feed in order：First each 10Kg of LDPE and LLDPE are added in cold mixer and stirred 10 minutes；
3) add shell powder and coupling agent is stirred 10 minutes；
4) PE waxes and zinc stearate co-blended is added to stir 10 minutes；
5) double screw extruder extruding pelletization cooling packing.
Weight shared by each component is as shown in table 6 in the degradative plastic film
Component and weight in degradative plastic film described in table 6
| Sequence number | Title | Unit | Consumption | Remarks |
| 1 | LDPE | Kg | 25 | |
| 2 | LLDPE | Kg | 20 | |
| 3 | M‐PE | Kg | 5 | |
| 4 | Degradable master batch | Kg | 12‐20 | Changed by degradation time requirement |
| 5 | Degraded filler | Kg | 25‐40 | |
| 6 | Antifoggant | Kg | 0.5 | |
| 7 | EBS | Kg | 1‐2 | Dispersed lubricant |
The occasion that current film-mulching technique is used is more, it is desirable to which the time difference of controllable degraded is larger.Drop too early
Solution can influence using effect, and degraded too late can influence next cycle to plough farming again.By above-mentioned formula prepare can
The degradative plastic film of control degradation time can adapt to different use occasions.
Degradative plastic film of the present invention has soil heat preservation, moisturizing, cover crop root is healthy and strong, prevent fertilizer loss, control
Make the various functions such as weedy and preventing disease and pest.It can involve the various farmings such as cultivated wheat, paddy rice, corn, vegetables, fruit tree
Thing, and can in vinyl house covering with plastic film.Specific effect is to improve yield, improving quality, increase benefit, shift to an earlier date and delay receipts
Obtain the phase.
Claims (9)
1. a kind of degradative plastic film for filler of being degraded containing string, it is characterised in that the degradative plastic film includes being used as mulch film base
The resin of matter, the degradable master batch for promoting Plastic-film disintegration, antifoggant, auxiliary agent, the degraded filler containing natural plant fibre powder.
2. according to claim 1 it is a kind of containing string degrade filler degradative plastic film, it is characterised in that it is described as ground
The resin of membrane matrix uses polyvinyl chloride（PVC）Or using by polyethylene（LDPE）, LLDPE（LLDPE）With
Metallocene PE（mPE）The hybrid resin that three kinds of resins are constituted, is determined according to the species of the resin as ground membrane matrix
The addition species of the auxiliary agent.
3. according to claim 1 it is a kind of containing string degrade filler degradative plastic film, it is characterised in that the degraded is filled out
The preparing raw material of material includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant and lubricant；It is wherein described
Natural plant fibre powder is using any one in powdered rice hulls, powder of straw, peanut shell powder and boll hull powder or two or more；Control institute
The particle diameter for stating natural plant fibre powder is more than 800 mesh, moisture≤3%.
4. according to claim 2 it is a kind of containing string degrade filler degradative plastic film, it is characterised in that when the conduct
Mulch film matrix resin uses polyvinyl chloride（PVC）When, the auxiliary agent includes plasticizer and PVC compound stabilizers, the plasticizer
For dioctyl adipate（DOA）, o-phthalic acid dibutyl ester（DOP）, dibutyl phthalate (DBP)（DBP）In epoxidized soybean oil
Any one or any two or more combinations；The PVC compound stabilizers are calcium-zinc composite stabilizing agent.
5. a kind of degradative plastic film for filler of being degraded containing string according to claim 4, it is characterised in that the degraded is female
Material includes polyvinyl chloride（PVC）, biodegradation agent, photodegradable aid, dispersant；The biodegradation agent includes polycaprolactone
（PCL）, poly-succinic fourth diester（PBS）And ATBC（TBC）, the photodegradable aid is ferric stearate, described scattered
Agent is double ethylene stearmides（EBS）；The degraded filler include degraded filler resin, natural plant fibre powder, coupling agent,
Dispersant and lubricant；Wherein, the degraded filler uses polyvinyl chloride with resin（PVC）, the natural plant fibre powder adopts
With the one or two in powdered rice hulls and powder of straw, the coupling agent uses silane coupler, and the dispersant is double using ethylene
Stearmide（EBS）, the lubricant uses HSt.
6. according to a kind of one of claim 1-5 degradative plastic films for filler of being degraded containing string, it is characterised in that described
Degradative plastic film also includes impact modifier and toner, wherein the impact modifier uses MBS resins；By weight, it is described
Parts by weight are shared by each component in degradative plastic film：Polyvinyl chloride（PVC）100 parts, 6-10 parts of MBS resins, dioctyl adipate
（DOA）5-6 parts, o-phthalic acid dibutyl ester（DOP）15-17 parts, dibutyl phthalate (DBP)（DBP）13-16 parts, epoxy soybean
Oily 5-7 parts, 2-2.5 parts of calcium-zinc composite stabilizing agent, 18-24 parts of degradable master batch, 20-26 parts of filler of degraded, antifoggant, 0.8-1.2
Part, 1-2 parts of toner.
7. according to claim 2 it is a kind of containing string degrade filler degradative plastic film, it is characterised in that when the conduct
When the resin of ground membrane matrix uses the hybrid resin, the auxiliary agent is dispersed lubricant；The degradable master batch includes polyethylene
（LDPE）, biodegradation agent, photodegradable aid, biodegradation material, bulking agent；The biodegradation agent is polyester branches derivative
With the polyester of polyadipate-terephthalic acid (TPA)-butanediol-terpolymer（PBAT）；The photodegradable aid is ferric stearate；Institute
Bulking agent is stated for the fourth fat of metatitanic acid four（TBT）.
8. according to claim 7 it is a kind of containing string degrade filler degradative plastic film, it is characterised in that the degraded is filled out
The preparing raw material of material includes degraded filler resin, natural plant fibre powder, coupling agent, dispersant and lubricant；Wherein, it is described
Degraded filler uses polyethylene with resin（LDPE）And LLDPE（LLDPE）Hybrid resin, and the mixing
Polyethylene in resin（LDPE）And LLDPE（LLDPE）Hybrid resin mass ratio be 1:1；The natural plant
Fibres powder uses the one or two in powdered rice hulls and powder of straw；The coupling agent uses silane coupler, the dispersant
Using zinc stearate, the lubricant uses Tissuemat E（PE waxes）.
9. according to a kind of one of claim 7-8 degradative plastic films for filler of being degraded containing string, it is characterised in that by weight
Amount is than counting, and parts by weight shared by each component are in the degradative plastic film：Polyethylene（LDPE）25 parts, LLDPE
（LLDPE）20 parts, metallocene PE（mPE）5 parts, 10-20 parts of degradable master batch, degraded 25-40 parts of filler, antifoggant 0.5-1
Part, double ethylene stearmides（EBS）1-2 parts.
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| CN107619529A (en) * | 2017-09-25 | 2018-01-23 | 李顺华 | Bio-based fully-degradable plastic, preparation method and application thereof |
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| CN114874637B (en) * | 2022-06-07 | 2023-01-13 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
| CN116987339A (en) * | 2023-09-26 | 2023-11-03 | 广东中洲包装材料科技有限公司 | Degradable bamboo fiber-based polymer material and preparation method thereof |
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Application publication date: 20170714 |