CN106479132B - A kind of degradation of plastic film master batch and the preparation method and application thereof - Google Patents
A kind of degradation of plastic film master batch and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to plastic film technical field, discloses a kind of degradation of plastic film master batch and preparation method thereof and 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%；Dispersing agent 0.5~5%；MWCNT is modified PHB 14~30%；Ferric stearate 2~7%；Plasticizer 1~5%；The total amount of said components is 100%.By mixing the above components evenly, melting extrusion obtains master batch of the present invention.Master batch of the present invention not only has excellent compatibility with non-polar polymers such as polyethylene, polypropylene, while can be applied to polyester, polycarbonate, ABS isopolarity polymer；And have light degradation and biodegradability, be applied to and prepare in plastic degradation film, film automatic classifying under oxygen-enriched and microorganism or natural lighting, it is discarded after film can be degraded digestion.
Description
Technical field
The invention belongs to plastic film technical field, in particular to a kind of degradation of plastic film master batch and preparation method thereof with
Preparing the application in plastic degradation film.
Background technique
Agricultural plastic film is mainly canopy film and mulch, additionally includes sunshade net, fly net, forage grass film and agricultural
Non-woven fabrics etc..Plastic film is widely used as the covering material of heliogreenhouse, vinyl house and various plastics Small plastic sheds.Plastics are thin
The dosage of film increasingly increases, its long degradation time is up to 200~300 years, and use causes serious to China's ecological environment
" white pollution ".There are two the approach for solving plastic film white pollution in the world at present, first is that recycled plastic film, second is that opening
Send out agricultural film degradable.But since China's mulch dosage and area coverage are big, recycling is difficult, therefore more practicable approach is pair
The exploitation and application of degradation plastic film.
The kind that the country has entered pilot scale or produced degradable plastic product in batches at present mainly has starch base, calcium carbonate to fill out
Several degradative plastics of adding type, modified PVA etc. ten.Application No. is the Chinese patent of 201410493794.X disclose report it is a kind of resistance to
Degradable PE film of high temperature lightfastness aging 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, master batch is finally squeezed out into blown film using plastic film blowing machine, it is resistance to obtain high temperature resistant
The degradable PE film of light aging.It is disclosed application No. is 201310110935 Chinese patent and reports a kind of oxygen barrier and degradable modeling
Expect film, raw material components and weight are respectively as follows: 100 parts of low density polyethylene (LDPE), and 50~70 parts of PBM masterbatch, pulullan polysaccharide 20
~40 parts, 2~4 parts of antioxidant, 0.5~1 part of ultraviolet absorbing agent.The extruding pelletization in double screw extruder obtains master batch, female
Grain is mixed with PBM degradable material, squeezes out blown film using plastic film blowing machine to get product.The PE master batch of foregoing invention patent report
It is only applicable to a certain specific substrate, there is no combine parental type high molecular weight compatibilizer and degradation to be incorporated in one by preparation so far
It rises and prepares a kind of degradation of plastic film master batch, the report for different substrate materials.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of plastic film
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 that providing above-mentioned degradation of plastic film master batch is preparing the application in plastic degradation film.
The purpose of the present invention is realized by following proposal:
A kind of degradation of plastic film master batch, the component including following mass percent:
In one of the embodiments, the matrix resin can for linear low density polyethylene, ultra-low density polyethylene,
In low density polyethylene (LDPE), medium density polyethylene and high density polyethylene (HDPE) any one or combinations thereof；Preferably low density polyethylene
Alkene.
In one of the embodiments, the response type compatilizer be Et-MAH-EA terpolymer, it is anhydride modified
SEBS and maleic anhydride are grafted any one in polyphenyl alkene (MAH-g-PS) or combinations thereof；Preferably anhydride modified SEBS.This
The response type compatilizer that invention uses is the polymer of a kind of same non-polar high polymer main chain Pc and active group composition.Due to it
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 or strong conjunction of object are closed, therefore good compatible role can be played.The base polyethylene of non-polar sidechain and master batch
Resin has a good compatibility, while the polar group of the compatilizer can also be with the polar group of the engineering plastics such as nylon, polyester
Group chemically reacts, and improves the compatibility of master batch and polarity engineering plastics.
Dispersing agent of the present invention is preferably TAS-2A novel lubricating dispersing agent.
Poly- beta-hydroxybutyric acid (PHB) is thermoplastic polyester, and there is storage energy, carbon source and reduction intracellular osmotic pressure etc. to make
With chemical structure is regular, and crystallinity is up to 60~80%, relatively denser, oxygen transmission rate is low, ultraviolet radiation resisting, tool optics are living
Property, but brittle, easy fracture.For this purpose, the present invention is right using the surface-treated multi-walled carbon nanotube (MWCNT) of silane coupling agent
PHB is modified.The modified PHB of MWCNT under the collaboration of ferric stearate, played master batch biodegrade and light degradation property, keep away
Exempt from that plastic film is exposed to soil surface and biodegradation rate is slow, or has been embedded in soil partially and can not see sunlight and cannot decompose
The case where.
Plasticizer of the present invention is preferably phthalic ester plasticizer, such as can be dioctyl phthalate
(DOP), dibutyl phthalate (DBP) etc..
The modified PHB of MWCNT of the present invention can be by including the following steps that method is prepared: first with silane coupling agent
Multi-walled carbon nanotube (MWCNT) is surface-treated, then with PHB blending extrusion, obtain the modified PHB of MWCNT.
Specifically it can comprise the following steps that
The ethanol solution of silane coupling agent is heated to 50~65 DEG C, MWCNT is added, modification is obtained by filtration in stirring
MWCNT；After being blended with PHB, melting extrusion obtains the modified PHB of MWCNT.
The present invention also provides a kind of preparation methods of above-mentioned degradation of plastic film master batch, by mixing the component in proportion
It closes, melting extrusion.
The mixing preferably mixes 10~30min in a high speed mixer.
The temperature of the melting extrusion is preferably 120~160 DEG C.
Master batch of the invention not only has good compatibility with non-polar polymers such as polyethylene, polypropylene, while can
Applied in polyester, polycarbonate, ABS isopolarity polymer, therefore can be applied to prepare in plastic degradation film.Can specifically it lead to
It crosses by mixed with polymers such as degradation of plastic film master batches and polyethylene, polyester or polycarbonate of the invention, using plastic membrane blowing
Machine squeezes out blown film to get the degradable plastic film of different substrate materials.
Degradation of plastic film master batch of the present invention has light degradation and biodegradability, and can be used for different substrate materials, so that
Plastic film under oxygen-enriched and microorganism or natural lighting can automatic classifying, it is discarded after film can be degraded digestion, finally
Generate carbon dioxide and water.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Reagent used in the following example can be obtained from commercial channel.
Embodiment 1:
(1) surface organic the processing of the modified PHB of MWCNT: is carried out to multi-walled carbon nanotube (MWCNT) with silane coupling agent
Processing.First the ethanol solution of silane coupling agent is heated to 55 DEG C in a water bath, is stirring evenly and then adding into metering
MWCNT is filtered while hot after stir process, it is dry after up to modified MWCNT.By PHB and modified MWCNT in mass ratio with 98:2's
After ratio mixing, melting extrusion obtains the modified PHB of MWCNT.
(2) by low density polyethylene (LDPE), Et-MAH-EA terpolymer, TAS-2A dispersing agent, MWCNT modified PHB, tristearin
Sour iron, plasticizer (DOP) are prepared with the mass percent ratio of 50:6:5:30:4:5, are mixed 30 minutes in a high speed mixer,
Then the melt blending in 120~160 DEG C of mixers, discharge after mixing and the master batch made.
(3) the plastic film Degradable master batch 2% that step (2) obtains is added to the plastic film prepared in polyester, room
It is 79% that the degradation rate in soil after 10 days is embedded under temperature.
Embodiment 2:
(1) processing of the modified PHB of MWCNT is the same as embodiment 1.
(2) composition that mixes linear low density polyethylene and low density polyethylene (LDPE) mass ratio 1:1, anhydride modified
The modified PHB of SEBS, TAS-2A dispersing agent, MWCNT, ferric stearate, plasticizer (DOP) are with the quality percentage of 80:2:1:14:2:1
It prepares, mixes in a high speed mixer 30 minutes, then the melt blending in 120~160 DEG C of mixers, is uniformly mixed than ratio
The master batch for discharging and making afterwards.
(3) the plastic film Degradable master batch that step (2) obtains is added to the plastic film prepared in polyester with 2%,
Being embedded in the degradation rate in soil after 10 days at room temperature is 85%.
Embodiment 3:
(1) processing of the modified PHB of MWCNT is the same as embodiment 1.
(2) composition, MAH-g-PS, TAS-2A for mixing low density polyethylene (LDPE) and high density polyethylene (HDPE) mass ratio 1:1
The modified PHB of dispersing agent, MWCNT, ferric stearate, plasticizer (DBP) are prepared with the mass percent ratio of 60:10:5:20:3:2,
It mixes 30 minutes in a high speed mixer, then the melt blending in 120~160 DEG C of mixers, discharges after mixing and make
The master batch.
(3) that plastic film Degradable master batch that step (2) obtains is added to the plastics prepared in polycarbonate with 2% is thin
Film, being embedded in the degradation rate in soil after 10 days at room temperature is 82%.
Embodiment 4:
(1) processing of the modified PHB of MWCNT is the same as embodiment 1.
(2) medium density polyethylene, Et-MAH-EA terpolymer and anhydride modified SEBS are mixed with mass ratio 1:1
The modified PHB of composition, TAS-2A dispersing agent, MWCNT, ferric stearate, plasticizer (DBP) are with the matter of 70:6.5:0.5:14:7:2
Amount percentage prepares, and mixes in a high speed mixer 30 minutes, then the melt blending in 120~160 DEG C of mixers, is mixed
The master batch for discharging and making after closing uniformly.
(3) that plastic film Degradable master batch that step (2) obtains is added to the plastics prepared in polyethylene with 2% is thin
Film, being embedded in the degradation rate in soil after 10 days at room temperature is 89%.
Embodiment 5:
(1) processing of the modified PHB of MWCNT is the same as embodiment 1.
(2) combination for mixing low low density polyethylene (LDPE), Et-MAH-EA terpolymer and MAH-g-PS mass ratio 1:1
The modified PHB of object, TAS-2A dispersing agent, MWCNT, ferric stearate, plasticizer (DOP) are with the mass percent of 65:5:3:20:5:2
Ratio prepares, in a high speed mixer mixing 30 minutes, then the melt blending in 120~160 DEG C of mixers, after mixing
The master batch for discharging and making.
(3) the plastic film Degradable master batch that step (2) obtains is added to the plastic film prepared in ABS, room with 2%
It is 84% that the degradation rate in soil after 10 days is embedded under temperature.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of degradation of plastic film master batch, it is characterised in that the component including following mass percent:
50~80 % of matrix resin；
2~10 % of response type compatilizer；
0.5~5 % of dispersing agent；
MWCNT is modified 14~30 % of PHB；
2~7 % of ferric stearate；
1~5 % of plasticizer；
The total amount of said components is 100 %；
The matrix resin is linear low density polyethylene, ultra-low density polyethylene, low density polyethylene (LDPE), medium density polyethylene
With in high density polyethylene (HDPE) any one or combinations thereof；The response type compatilizer is Et-MAH-EA terpolymer, acid
In anhydride modification SEBS and maleic anhydride grafted polystyrene any one or combinations thereof.
2. degradation of plastic film master batch according to claim 1, it is characterised in that: the dispersing agent is TAS-2A lubrication
Dispersing agent；The plasticizer is phthalic ester plasticizer.
3. degradation of plastic film master batch according to claim 1, it is characterised in that: the matrix resin is poly- for low-density
Ethylene；The response type compatilizer is anhydride modified SEBS；The plasticizer is dioctyl phthalate and adjacent benzene two
At least one of formic acid dibutyl ester.
4. degradation of plastic film master batch according to claim 1, it is characterised in that: the modified PHB of the MWCNT is by including
Following steps method is prepared: being surface-treated first with silane coupling agent to multi-walled carbon nanotube, then is blended and squeezes with PHB
Out, the modified PHB of MWCNT is obtained.
5. degradation of plastic film master batch according to claim 1, it is characterised in that: the modified PHB of the MWCNT is by specific
Include the following steps that method is prepared: the ethanol solution of silane coupling agent being heated to 50~65 DEG C, MWCNT is added,
Stirring, is obtained by filtration modified MWCNT；After being blended with PHB, melting extrusion obtains the modified PHB of MWCNT.
6. a kind of preparation method of the described in any item degradation of plastic film master batches of Claims 1 to 5, it is characterised in that pass through by
The component mixes in proportion, melting extrusion.
7. the preparation method of degradation of plastic film master batch according to claim 6, it is characterised in that: described is mixed into
10~30 min are mixed in high-speed mixer；The temperature of the melting extrusion is 120~160 DEG C.
8. the described in any item degradation of plastic film master batches of Claims 1 to 5 are preparing the application in plastic degradation film.
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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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