CN106479132A - A kind of degradation of plastic film master batch and preparation method and application - Google Patents
A kind of degradation of plastic film master batch and preparation method and application Download PDFInfo
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- 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
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- 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
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- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
- C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- 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
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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Abstract
The invention belongs to plastic sheeting technical field, discloses a kind of degradation of plastic film master batch and preparation method thereof and is preparing the application in plastic degradation film.Degradation of plastic film master batch of the present invention includes the component of following mass percent:Matrix resin 50~80%;Response type compatilizer 2~10%;Dispersant 0.5~5%;MWCNT modification PHB 14~30%;Ferric stearate 2~7%;Plasticizer 1~5%;The total amount of said components is 100%.Master batch of the present invention melt extrudes and obtains by mixing said components.Master batch of the present invention not only has excellent compatibility with non-polar polymers such as polyethylene, polypropylene, while can be applicable to polyester, Merlon, ABS isopolarity polymer;And possess light degradation and biodegradability, be applied to and prepare in plastic degradation film, film automatic classifying under oxygen-enriched and microorganism or natural lighting, discarded after film can be degraded digestion.
Description
Technical field
The invention belongs to plastic sheeting technical field, more particularly to a kind of degradation of plastic film master batch and preparation method thereof with
Application in plastic degradation film is prepared.
Background technology
Agricultural plastic film is mainly canopy film and mulch film, additionally includes sunshade net, fly net, forage grass film and agricultural
Non-woven fabrics etc..Plastic sheeting is widely used as the covering material of heliogreenhouse, vinyl house and various plastics Small plastic shed.Plastics are thin
The consumption of film increasingly increases, and its degradation time long is up to 200~300 years, and which is serious using causing to China's ecological environment
" white pollution ".The approach for solving plastic sheeting white pollution at present in the world has two, and one is recycled plastic film, and two are out
Send out agricultural film degradable.But due to China's mulch film consumption and area coverage greatly, difficulty is reclaimed, therefore more practicable approach is right
The exploitation of degradation plastic film and application.
The country has been enter into pilot scale or the kind of batch production degradable plastic product at present mainly has starch base, calcium carbonate to fill out
Plus several degradative plastics of type, modified PVA etc. ten.The Chinese patent of Application No. 201410493794.X disclose report a kind of resistance to
Aging degradable PE film of high temperature lightfastness and preparation method thereof, PE film includes following components:PE, antioxidant, auxiliary antioxidant, light are steady
Determine agent, polyester fiber, silica white, vegetable oil, butyl titanate, sorbic acid, hydroxypropul starch, hydroxypropyl methyl cellulose.First lead to
Double screw extruder extruding pelletization is crossed, master batch is obtained, finally master batch is extruded blown film using plastic film blowing machine, obtain high temperature resistant resistance to
The degradable PE film of light aging.The Chinese patent of Application No. 201310110935 is disclosed and reports a kind of oxygen barrier and degradable modeling
Material film, its raw material components and weight are respectively:100 parts of low density polyethylene (LDPE), 50~70 parts of PBM masterbatch, pulullan polysaccharide 20
~40 parts, 2~4 parts of antioxidant, 0.5~1 part of ultra-violet absorber.Extruding pelletization in double screw extruder, obtains master batch, female
Grain is mixed with PBM degradable material, is extruded blown film using plastic film blowing machine, is obtained final product product.The PE master batch of foregoing invention patent report
A certain specific base material is only applicable to, be there is no so far and combined one with reference to parental type high molecular weight compatibilizer and degraded by preparation
Rise and a kind of degradation of plastic film master batch is prepared, for the report of different substrate materials.
Content of the invention
In order to overcome the shortcoming of above-mentioned prior art and deficiency, the primary and foremost purpose of the present invention is to provide a kind of plastic sheeting
Degradation master batch.
Another object of the present invention is to provide a kind of preparation method of above-mentioned degradation of plastic film master batch.
Still a further object of the present invention is to provide application of the above-mentioned degradation of plastic film master batch in plastic degradation film is prepared.
The purpose of the present invention is realized by following proposal:
A kind of degradation of plastic film master batch, including the component of following mass percent:
Wherein in one embodiment, described matrix resin can for LLDPE, ultra-low density polyethylene,
Any one in low density polyethylene (LDPE), medium density polyethylene and high density polyethylene (HDPE) or its combination;Preferably low density polyethylene
Alkene.
Wherein in one embodiment, described response type compatilizer is Et-MAH-EA terpolymer, anhydride modified
Any one in SEBS and maleic anhydride grafting polyphenyl alkene (MAH-g-PS) or its combination;Preferably anhydride modified SEBS.This
The response type compatilizer that invention is adopted is the polymer of a kind of same non-polar high polymer main chain Pc and active group composition.Due to which
Non-polar high polymer main body can be compatible with the non-polar polymer in blend, and polar group can be poly- with the polarity of blend
The active group reaction of compound or strong conjunction, therefore good compatible role can be played.Non-polar sidechain and the base polyethylene of master batch
Resin has good compatibility, while the polar group of the compatilizer can also be with the polar group of the engineering plastics such as nylon, polyester
There is chemical reaction in group, improve the compatibility of master batch and polarity engineering plastics.
Dispersant of the present invention is preferably TAS-2A novel lubricating dispersant.
Poly- beta-hydroxybutyric acid (PHB) is thermoplastic polyester, makees with storage energy, carbon source and reduction intracellular osmotic pressure etc.
With chemical constitution is regular, degree of crystallinity up to 60~80%, and relatively denser, oxygen transmission rate is low, ultraviolet radiation resisting, tool optics are lived
Property, but brittle, easy fracture.For this purpose, the present invention is right using the surface-treated multi-walled carbon nano-tubes (MWCNT) of silane coupler
PHB is in addition modified.Under the collaboration of MWCNT modification PHB and ferric stearate, the biodegradable and light degradation property of master batch is played, has been kept away
Exempt from that plastic sheeting is exposed to soil surface and biodegradation rate is slow, or be embedded in soil and partly can not see sunlight and can not decompose
Situation.
Plasticizer of the present invention is preferably phthalic ester plasticizer, can be such as dioctyl phthalate
(DOP), dibutyl phthalate (DBP) etc..
MWCNT modification PHB of the present invention can be prepared by the method for comprising the following steps:First with silane coupler
Multi-walled carbon nano-tubes (MWCNT) is surface-treated, then with PHB blending extrusion, obtain MWCNT modification PHB.
Following steps specifically may include:
The ethanol solution of silane coupler is heated to 50~65 DEG C, MWCNT is added, stir, be filtrated to get modification
MWCNT;After PHB blending, melt extrude, obtain MWCNT modification PHB.
The present invention also provides a kind of preparation method of above-mentioned degradation of plastic film master batch, by mixing the component in proportion
Close, melt extrude.
Described mixing is preferably and mixes 10~30min in high-speed mixer.
The described temperature for melt extruding is preferably 120~160 DEG C.
The master batch of the present invention not only has good compatibility with non-polar polymers such as polyethylene, polypropylene, while can
It is applied in polyester, Merlon, ABS isopolarity polymer, therefore can be applicable to prepare in plastic degradation film.Can specifically lead to
Cross by the degradation of plastic film master batch of the present invention and the mixed with polymers such as polyethylene, polyester or Merlon, using plastic membrane blowing
Blown film extruded by machine, obtains final product the degradable plastic film of different substrate materials.
Degradation of plastic film master batch of the present invention possesses light degradation and biodegradability, and can be used for different substrate materials so that
Plastic sheeting under oxygen-enriched and microorganism or natural lighting can automatic classifying, discarded after film can be degraded digestion, finally
Generate carbon dioxide and water.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Reagent used in the following example all can be obtained from commercial channel.
Embodiment 1:
(1) process of MWCNT modification PHB:Surface organic is carried out to multi-walled carbon nano-tubes (MWCNT) with silane coupler
Process.First the ethanol solution of silane coupler is heated to 55 DEG C in a water bath, is stirring evenly and then adding into metering
MWCNT, is filtered after stir process while hot, obtains final product modified MWCNT after drying.By PHB and modification MWCNT in mass ratio with 98:2
After ratio mixing, melt extrude and obtain MWCNT modification PHB.
(2) by low density polyethylene (LDPE), Et-MAH-EA terpolymer, TAS-2A dispersant, MWCNT modification PHB, tristearin
Sour iron, plasticizer (DOP) are with 50:6:5:30:4:5 mass percent ratio is prepared, and is mixed 30 minutes in high-speed mixer,
Then melt blending in 120~160 DEG C of banburies, discharges after mixing and the master batch of system.
(3) the plastic sheeting Degradable master batch 2% for obtaining step (2) is added to the plastic sheeting that prepare in polyester, room
It is 79% to be embedded in the degradation rate in soil after 10 days under temperature.
Embodiment 2:
(1) process of MWCNT modification PHB is with embodiment 1.
(2) by LLDPE and low density polyethylene (LDPE) mass ratio 1:The composition, anhydride modified of 1 mixing
SEBS, TAS-2A dispersant, MWCNT modification PHB, ferric stearate, plasticizer (DOP) are with 80:2:1:14:2:1 percent mass
Prepare than ratio, mix 30 minutes in high-speed mixer, then melt blending in 120~160 DEG C of banburies, mixes
The master batch for discharging afterwards and making.
(3) the plastic sheeting Degradable master batch for obtaining step (2) is added to, with 2%, the plastic sheeting that prepare in polyester,
It is 85% to be embedded in the degradation rate in soil after 10 days under room temperature.
Embodiment 3:
(1) process of MWCNT modification PHB is with embodiment 1.
(2) by low density polyethylene (LDPE) and high density polyethylene (HDPE) mass ratio 1:The composition of 1 mixing, MAH-g-PS, TAS-2A
Dispersant, MWCNT modification PHB, ferric stearate, plasticizer (DBP) are with 60:10:5:20:3:2 mass percent ratio is prepared,
Mix in high-speed mixer 30 minutes, then melt blending in 120~160 DEG C of banburies, discharges after mixing and make
The master batch.
(3) the plastic sheeting Degradable master batch that step (2) is obtained with 2% be added in Merlon prepare plastics thin
Film, it is 82% to be embedded in the degradation rate in soil after 10 days under room temperature.
Embodiment 4:
(1) process of MWCNT modification PHB is with embodiment 1.
(2) by medium density polyethylene, Et-MAH-EA terpolymer and anhydride modified SEBS with mass ratio 1:1 mixing
Composition, TAS-2A dispersant, MWCNT modification PHB, ferric stearate, plasticizer (DBP) are with 70:6.5:0.5:14:7:2 matter
Amount percentage is prepared, and is mixed 30 minutes in high-speed mixer, and then melt blending in 120~160 DEG C of banburies, mixes
The master batch for closing uniform rear discharging and making.
(3) the plastic sheeting Degradable master batch that step (2) is obtained with 2% be added in polyethylene prepare plastics thin
Film, it is 89% to be embedded in the degradation rate in soil after 10 days under room temperature.
Embodiment 5:
(1) process of MWCNT modification PHB is with embodiment 1.
(2) by low low density polyethylene (LDPE), Et-MAH-EA terpolymer and MAH-g-PS mass ratio 1:The combination of 1 mixing
Thing, TAS-2A dispersant, MWCNT modification PHB, ferric stearate, plasticizer (DOP) are with 65:5:3:20:5:2 mass percent
Ratio is prepared, mixing 30 minutes in high-speed mixer, then melt blending in 120~160 DEG C of banburies, after mixing
The master batch for discharging and making.
(3) the plastic sheeting Degradable master batch for obtaining step (2) is added to the plastic sheeting that prepare in ABS, room with 2%
It is 84% to be embedded in the degradation rate in soil after 10 days under temperature.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change that is made under principle, modification, replacement, combine, simplify,
Equivalent substitute mode is all should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of degradation of plastic film master batch, it is characterised in that including the component of following mass percent:
2. degradation of plastic film master batch according to claim 1, it is characterised in that:Described matrix resin is linearly low close
Degree polyethylene, ultra-low density polyethylene, low density polyethylene (LDPE), in medium density polyethylene and high density polyethylene (HDPE) any one or
Its combination.
3. degradation of plastic film master batch according to claim 1, it is characterised in that:Described response type compatilizer is Et-
Any one in MAH-EA terpolymer, anhydride modified SEBS and maleic anhydride grafting polyphenyl alkene or its combination.
4. degradation of plastic film master batch according to claim 1, it is characterised in that:Described dispersant is that TAS-2A is new
Lubrication dispersing agent;Described plasticizer is phthalic ester plasticizer.
5. degradation of plastic film master batch according to claim 1, it is characterised in that:Described matrix resin is poly- for low-density
Ethene;Described response type compatilizer is anhydride modified SEBS;Described plasticizer is dioctyl phthalate and adjacent benzene two
At least one in formic acid dibutyl ester.
6. degradation of plastic film master batch according to claim 1, it is characterised in that:Described MWCNT modification PHB is by including
Following steps method is prepared:Multi-walled carbon nano-tubes is surface-treated first with silane coupler, then squeezes with PHB blending
Go out, obtain MWCNT modification PHB.
7. degradation of plastic film master batch according to claim 1, it is characterised in that:Described MWCNT modification PHB is by concrete
The method of comprising the following steps is prepared:The ethanol solution of silane coupler is heated to 50~65 DEG C, MWCNT is added,
Stirring, is filtrated to get modified MWCNT;After PHB blending, melt extrude, obtain MWCNT modification PHB.
8. the preparation method of the degradation of plastic film master batch described in a kind of any one of claim 1~7, it is characterised in that by will
The component mixes in proportion, melt extrudes.
9. the preparation method of degradation of plastic film master batch according to claim 8, it is characterised in that:Described is mixed into
Mix 10~30min in high-speed mixer;The described temperature for melt extruding is 120~160 DEG C.
10. application of the degradation of plastic film master batch described in any one of claim 1~7 in plastic degradation film is prepared.
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Cited By (5)
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CN106957472A (en) * | 2017-03-20 | 2017-07-18 | 兰州鑫银环橡塑制品有限公司 | A kind of novel high-strength environment protection modification material for adding CNT and preparation method thereof |
CN109401002A (en) * | 2018-09-26 | 2019-03-01 | 天津泽恒包装制品有限公司 | A kind of PE high glues the preparation method of protective film masterbatch |
CN110511471A (en) * | 2019-09-23 | 2019-11-29 | 安徽超星新材料科技有限公司 | A kind of environment-friendly type antibiotic plastic film and its preparation process |
CN111690228A (en) * | 2020-06-24 | 2020-09-22 | 深圳市同益实业股份有限公司 | Degradable high-brightness white silver spraying-free material and preparation method thereof |
CN112795072A (en) * | 2021-01-19 | 2021-05-14 | 洛阳绿之汇塑料降解科技有限公司 | Natural light-microorganism dual-degradation master batch and preparation method thereof |
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CN111690228A (en) * | 2020-06-24 | 2020-09-22 | 深圳市同益实业股份有限公司 | Degradable high-brightness white silver spraying-free material and preparation method thereof |
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