CN109320828A - A kind of environment degradable courier bag thin-film material and preparation method thereof - Google Patents
A kind of environment degradable courier bag thin-film material and preparation method thereof Download PDFInfo
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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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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a kind of environment degradable courier bag thin-film materials and preparation method thereof.This kind degradation courier bag thin-film material is made of starch, polylactic acid, hexane diacid-terephthalic acid-butylene terephthalate copolymer, coupling agent, talcum powder, degradation of promoter, color masterbatch and linear low density polyethylene.By 5%~10% starch, 10%~30% talcum powder, 0.01%~5% degradation of promoter, 20%~40% polylactic acid, 40%~60% hexane diacid-terephthalic acid-butylene terephthalate copolymer, 0.1%~0.5% vinyltrimethoxysilane and 0~20% linear low density polyethylene carry out mixed at high speed, and degradable material is made；By the degradable material of 8%~30% weight percent, 65%~85% linear low density polyethylene and 2%~7% color masterbatch mix, courier bag thin-film material is made, after courier bag is made.This courier bag can fast degradation after complete.
Description
Technical field
The present invention relates to express delivery packing film Material Fields, and in particular to a kind of environment degradable courier bag thin-film material and its
Preparation method.
Background technique
On June 1st, 2008, country, which has promulgated, forbids producing, selling and uying in China thickness less than 0.025 milli
The plastic shopping bag of rice；Plastic shopping bag paid utilization system is carried out in the commodity retails place such as all supermarkets, market, country fair
Degree, the use of polybag have obtained a degree of containment.However, the fast development of express delivery, brings the plastic bag for being difficult to estimate
Fill the consumption figure of product.According to statistics, China's express delivery amount in 2017 consumes Polywoven Bag 29.6 hundred million, polybag up to 31,300,000,000
82.6 hundred million, 169.5 meters of adhesive tape.Express delivery is packed due to using excessive adhesive tape, and which results in express delivery polybags to be difficult to recycle,
It is effectively treated if these plastic refuses are unable to get, will be a serious ecological pollution.
Summary of the invention
For solve the reluctant problem of shopping bag, the present invention provide it is a kind of by change prepare thin-film material formula and
Dosage finally makes courier bag thin-film material after losing its use value, and fast degradation environment degradable is fast in the natural environment
Pass bag thin-film material and preparation method thereof.
Technical solution of the present invention:
A kind of environment degradable courier bag thin-film material, thin-film material include the raw material of following parts by weight: 120 parts of degradable materials,
170 parts of linear low density polyethylene and 10 parts of color masterbatch；10 parts of color masterbatch include 5 parts of White color masterbatches and 5 parts of black color masterbatch；
The degradable material includes the raw material of following weight percentage: 5%~10% starch, 10%~30% talcum powder,
0.01%~5% degradation of promoter, 20%~40% polylactic acid, 40%~60% hexane diacid-terephthalic acid-butylene terephthalate are total
Polymers, 0.1%~0.5% coupling agent and 0~20% linear low density polyethylene.
Further, the coupling agent is vinyltrimethoxysilane, methyltrimethoxysilane, triethanolamine boric acid
One of ester, four n-propyl zirconates, distearyl acyl-oxygen aluminum isopropoxide acid esters and aminopropyl triethoxysilane and its with
On.
Further, the degradation of promoter is copper compound, iron compound, titanium compound, cerium compound, cobalt chemical combination
In object, lanthanum compound and praseodymium compound it is a kind of and its more than.
Further, when the courier bag of production is with a thickness of 30 microns, the mixture of starch and talcum powder is crossed into 600 purposes
Sieve, tailing over is 0~10%, and by screenings after the sieve of 800 mesh, tailing over is 5%~30%；
When the courier bag of production is with a thickness of 40 microns, the mixture of starch and talcum powder crosses 400 sieve, tail over as 0~
10%, by screenings after the sieve of 500 mesh, tailing over is 5%~30%；
When the courier bag of production is with a thickness of 50 microns, the mixture of starch and talcum powder is crossed into 325 mesh sieve, tail over as 0~
10%, by screenings after the sieve of 400 mesh, tailing over is 5%~30%.
Further, a kind of preparation method of environment degradable courier bag thin-film material, by load weighted starch, talcum powder and
Degradation of promoter is put into heating stirring machine and is stirred, and stirs 3~4min, then by polylactic acid, adipic acid-terephthalic acid (TPA)-
Butanediol ester copolymer, coupling agent and linear low density polyethylene are put into heating stirring machine and are mixed, and mixing time 6 ~
Degradable material is made using twin-screw extruder pelletizer in 8min；
10 parts of degradable materials, 85 parts of linear low density polyethylene and 5 parts of White color masterbatches are mixed, it is mechanical to be put into three-layer co-extruded blown film
In the hopper of interior outer layer extruder；
In the hopper for the middle layer extruder that 100 parts of degradable materials are put into three-layer co-extruded blown film machinery；
10 parts of degradable materials, 85 parts of linear low density polyethylene and 5 parts of black color masterbatch are mixed, it is mechanical to be put into three-layer co-extruded blown film
In the hopper of interior inner layer extruder；Three extruders squeeze out simultaneously, and every layer of extrusion output is identical, by film head, blow molding, at
For courier bag thin-film material.
Further, the revolving speed of the heating stirring machine is 500 ~ 600rpm, and whipping temp is 50 DEG C ~ 60 DEG C.
Further, the screw slenderness ratio L/D of the twin-screw extruder pelletizer is 40 ~ 50, and pelletization stage temperature is 155
℃~185℃。
Percentage composition of the invention is the percentage composition of weight.
Described tail over is to stay in the percentage composition of the substance above sieve, screenings is logical during sieve sieve
The substance that sieve of sifting out down.
Beneficial effects of the present invention:
The present invention by preparing material add particular fineness starch and talcum powder after, except be able to satisfy express delivery use it is basic
Outside demand, after the mission for completing express delivery, courier bag thin-film material in the natural environment, can be carried out quick photooxidative degradation,
Thermal oxidative degradation, and in compost or microorganism place abundant, biodegrade is carried out, carbon dioxide, water is finally degraded to and lacks
Humus is measured, the pollution to environment is reduced.
In order to meet express transportation in the process to the needs of plastic film packaging material function, by multifrequency nature material blown film
And co-extrusion is together, forms multi-functional plastic film.The purpose of co-extrusion film blowing machine is exactly the advantages of playing multiple material,
Evade some disadvantages of single material or single layer inflation film manufacturing machine.The present invention is blown using three-layer co-extruded, and yield is high, product is plasticized
Good, low energy consumption, advantage easy to operate thoroughly solve film scollop, scallop and winding size first order issue, make in product quality
One New step.The film produced has that puncture-resistant, high tenacity, the fervent property of low temperature be good, compound securely good, Anti-curling.
This film can be widely applied to weight packaging due to its good barrier property, fresh-keeping, damp proof, frost protection, oxygen barrier, oil resistant.It is such as various fresh
Fruit, meat product, pickles, fresh milk, liquid beverage, medical supplies etc..
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1:
(A) degradable material formula (kg):
Starch (by 600 mesh sieve, tails over 8%, screenings is passed through to 800 mesh sieve again, tail over 30%): 5
Talcum powder (by 600 mesh sieve, tails over 2%, screenings is passed through to 800 mesh sieve again, tail over 10%): 10
Vinyltrimethoxysilane: 0.05
Four n-propyl zirconates: 0.05
Diethyldithioposphoric acid iron: 0.01
Polylactic acid: 40
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 44.89
(B) prepared by degradable material:
Step 1: load weighted starch, talcum powder, four n-propyl zirconates and vinyltrimethoxysilane to be put into heating and stir
It mixes in machine and is mixed, the revolving speed of heating stirring machine is 500rpm, 50 ~ 60 DEG C of whipping temp, mixing time 3min.
Step 2: by load weighted diethyldithioposphoric acid iron, polylactic acid and adipic acid-terephthalic acid (TPA)-butanediol
Ester copolymer is put into heating stirring machine and continuess to mix, and the revolving speed of heating stirring machine is 500rpm, and whipping temp is 50 ~ 60 DEG C,
Mixing time is 6min.
Step 3: mixture is granulated in twin-screw extruder pelletizer, degradable material is prepared.Twin-screw extruder is made
The screw slenderness ratio L/D of grain machine is 40, and pelletization stage temperature is 155 ~ 165 DEG C.
(C) courier bag film preparation:
Cladding material: 10 parts of degradable materials, 5 parts of White color masterbatches, 85 parts of linear low density polyethylene；
Middle layer material: 100 parts of degradable materials；
Inner layer material: 10 parts of degradable materials, 5 parts of black color masterbatch, 85 parts of linear low density polyethylene.
By cladding material, middle layer material and inner layer material pour into the outer layer extruder of three-layer co-extruded inflation film manufacturing machine, middle layer respectively
Extruder and inner layer extruder funnel, squeeze out simultaneously, and every layer of extrusion output is identical, by die head, are blow molded into a thickness of 30 microns
Courier bag film.
Embodiment 2:
(A) degradable material formula (kg):
Starch (by 400 mesh sieve, tails over 0, screenings is passed through to 500 mesh sieve again, tail over 5%): 5
Talcum powder (by 400 mesh sieve, tails over 0, screenings is passed through to 500 mesh sieve again, tail over 5%): 10
Vinyltrimethoxysilane: 0.3
Cerium stearate: 0.3
Polylactic acid: 24.6
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 60
(B) prepared by degradable material:
It is mixed step 1: load weighted starch, talcum powder and vinyltrimethoxysilane are put into heating stirring machine,
The revolving speed of heating stirring machine be 550rpm, 50 ~ 60 DEG C of whipping temp, mixing time 3min.
Step 2: load weighted cerium stearate, polylactic acid and hexane diacid-terephthalic acid-butylene terephthalate copolymer are put
Enter and continuesd to mix in heating stirring machine, the revolving speed of heating stirring machine is 550rpm, and whipping temp is 50 ~ 60 DEG C, and mixing time is
7min。
Step 3: mixture is granulated in twin-screw extruder pelletizer, degradable material is prepared.Twin-screw extruder is made
The screw slenderness ratio L/D of grain machine is 45, and pelletization stage temperature is 175 ~ 185 DEG C.
(C) courier bag film preparation:
Cladding material: 20% degradable material, 5% White color masterbatch, 75% linear low density polyethylene；
Middle layer material: 100% degradable material；
Inner layer material: 20% degradable material, 5% black color masterbatch, 75% linear low density polyethylene.
By cladding material, middle layer material and inner layer material pour into the outer layer extruder of three-layer co-extruded inflation film manufacturing machine, middle layer respectively
Extruder and inner layer extruder funnel, squeeze out simultaneously, and every layer of extrusion output is identical, by die head, are blow molded into a thickness of 40 microns
Courier bag film.
Embodiment 3:
(A) degradable material formula (kg):
Starch (by 400 mesh sieve, tails over 5%, screenings is passed through to 500 mesh sieve again, tail over 15%): 5
Talcum powder (by 400 mesh sieve, tails over 5%, screenings is passed through to 500 mesh sieve again, tail over 15%): 10
Vinyltrimethoxysilane: 0.3
Cerium stearate: 0.3
Polylactic acid: 24.6
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 60
(B) degradable material preparation, outer layer, middle layer and inner layer material composition and courier bag film preparation and embodiment 2 are identical.Blow molding
Molding courier bag film thickness is 40 microns.
Embodiment 4:
(A) degradable material formula (kg):
Starch (by 400 mesh sieve, tails over 10%, screenings is passed through to 500 mesh sieve again, tail over 30%): 5
Talcum powder (by 400 mesh sieve, tails over 10%, screenings is passed through to 500 mesh sieve again, tail over 30%): 10
Vinyltrimethoxysilane: 0.3
Cerium stearate: 0.3
Polylactic acid: 24.6
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 60
(B) degradable material preparation, outer layer, middle layer and inner layer material composition and courier bag film preparation and embodiment 2 are identical.Blow molding
Molding courier bag film thickness is 40 microns.
Embodiment 5:
(A) degradable material formula (kg):
Starch (by 400 mesh sieve, tails over 5%, screenings is passed through to 500 mesh sieve again, tail over 20%): 10
Talcum powder (500 mesh screen residues 20%, 400 mesh screen residues 5%): 20
Aminopropyl triethoxysilane: 0.5
Lauric acid manganese: 2.5
Diethyldithioposphoric acid iron: 2.5
Polylactic acid: 20
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 40
Linear low density polyethylene: 4.5
(B) degradable material prepares courier bag film preparation.
It is carried out step 1: load weighted starch, talcum powder and aminopropyl triethoxysilane are put into heating stirring machine
Mixing, the revolving speed of heating stirring machine are 600rpm, and whipping temp is 50 ~ 60 DEG C, mixing time 4min.
Step 2: by load weighted lauric acid manganese, diethyldithioposphoric acid iron, polylactic acid, linear low density polyethylene
It is put into heating stirring machine and continuess to mix with hexane diacid-terephthalic acid-butylene terephthalate copolymer, the revolving speed of heating stirring machine is
600rpm, whipping temp are 50 ~ 60 DEG C, mixing time 8min.
Step 3: mixture is granulated in twin-screw extruder pelletizer, degradable material is prepared.Twin-screw extruder is made
The screw slenderness ratio L/D of grain machine is 50, and pelletization stage temperature is 175 ~ 185 DEG C.
Courier bag film preparation:
Degradable material preparation, outer layer, middle layer and inner layer material composition and courier bag film preparation and embodiment 2 are identical.It is blow molded into
The courier bag film thickness of type is 50 microns
Embodiment 6
(A) degradable material formula (kg):
Starch (400 mesh screen residues 20%, 400 mesh screen residues 5%): 5
Talcum powder (500 mesh screen residues 20%, 400 mesh screen residues 5%): 10
Aminopropyl triethoxysilane: 0.1
Lauric acid manganese: 4.9
Polylactic acid: 20
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 40
Linear low density polyethylene: 20
(B) degradable material prepares courier bag film preparation.
It is carried out step 1: load weighted starch, talcum powder and aminopropyl triethoxysilane are put into heating stirring machine
Mixing, the revolving speed of heating stirring machine are 550rpm, and whipping temp is 50 ~ 60 DEG C, mixing time 3.5min.
Step 2: by load weighted lauric acid manganese, polylactic acid, linear low density polyethylene and adipic acid-terephthalic acid (TPA)-
Butanediol ester copolymer is put into heating stirring machine and continuess to mix, and the revolving speed of heating stirring machine is 550rpm, whipping temp 50 ~ 60
DEG C, mixing time 7min.
Step 3: mixture is granulated in twin-screw extruder pelletizer, degradable material is prepared.Twin-screw extruder is made
The screw slenderness ratio L/D of grain machine is 50, and pelletization stage temperature is 170 ~ 185 DEG C.
(C) courier bag film preparation:
Degradable material preparation, outer layer, middle layer and inner layer material composition and courier bag film preparation and embodiment 2 are identical.It is blow molded into
The courier bag film thickness of type is 50 microns
Embodiment 7
(A) degradable material formula (kg):
Starch (400 mesh screen residues 20%, 400 mesh screen residues 5%): 5
Talcum powder (500 mesh screen residues 20%, 400 mesh screen residues 5%): 30
Aminopropyl triethoxysilane: 0.3
Lauric acid manganese: 2.7
Polylactic acid: 20
Hexane diacid-terephthalic acid-butylene terephthalate copolymer: 40
Linear low density polyethylene: 2
(B) degradable material prepares courier bag film preparation.
It is carried out step 1: load weighted starch, talcum powder and aminopropyl triethoxysilane are put into heating stirring machine
Mixing, the revolving speed of heating stirring machine are 600rpm, and whipping temp is 50 ~ 60 DEG C, mixing time 4min.
Step 2: by load weighted lauric acid manganese, polylactic acid, linear low density polyethylene and adipic acid-terephthalic acid (TPA)-
Butanediol ester copolymer is put into heating stirring machine and continuess to mix, and the revolving speed of heating stirring machine is 600rpm, and whipping temp is 50 ~
60 DEG C, mixing time 8min.
Step 3: mixture is granulated in twin-screw extruder pelletizer, degradable material is prepared.Twin-screw extruder is made
The screw slenderness ratio L/D of grain machine is 50, and pelletization stage temperature is 175 ~ 185 DEG C.
(C) courier bag film preparation:
Degradable material preparation, outer layer, middle layer and inner layer material composition and courier bag film preparation and embodiment 2 are identical.It is blow molded into
The courier bag film thickness of type is 50 microns.
Experimental example 1:
Film in embodiment 1 ~ 5 is irradiated under ultraviolet light.Using 340nm fluorescent tube, the irradiation intensity under 340nm wavelength
For (0.78 ± 0.12) W/m2nm。
Table 1 is the relationship of mulch irradiation time and longitudinal elongation at break rate.
By embodiment 2,3 and 4 prepare film between comparison it has been observed that
In all identical situation of other conditions, we change the starch of addition and tailing over for talcum powder, then tail over bigger, process
After a period of time irradiates, elongation at break is smaller.It is mainly bigger due to tailing over, then large-sized starch and talcum particles
Shared ratio is more, and after illumination after a period of time, the aperture formed on film is bigger, and elongation at break is caused to be got over
It is small.
Experimental example 2:
By in embodiment 1 ~ 5 courier bag film and compost mix, be put into container, carry out indoor stack under dark or dim light
Fertilizer test.Keeping temperature is 58oC±2oC, the moisture content of mixture are 50%.Table 2 is the 4th, 8,12,16 week courier bag film
Elongation.
2 courier bag film compost time (week) of table and longitudinal elongation at break rate (%)
By embodiment 2,3 and 4 prepare film between comparison it has been observed that
In all identical situation of other conditions, we change the starch of addition and tailing over for talcum powder, then tail over bigger, big grain
Ratio shared by the starch and talcum particles of diameter is more, bigger in the aperture after compost after a period of time, formed on film,
Elongation at break is smaller.
After compost 16 weeks, elongation at break 0 illustrates to be degraded into broken film prepared by embodiment 4 and 5
Piece.
Claims (7)
1. a kind of environment degradable courier bag thin-film material, it is characterised in that: thin-film material includes the raw material of following parts by weight:
120 parts of degradable materials, 170 parts of linear low density polyethylene and 10 parts of color masterbatch；10 parts of color masterbatch include 5 parts of black color masterbatch and 5
Part White color masterbatch；
The degradable material includes the raw material of following weight percentage: 5%~10% starch, 10%~30% talcum powder,
0.01%~5% degradation of promoter, 20%~40% polylactic acid, 40%~60% hexane diacid-terephthalic acid-butylene terephthalate are total
Polymers, 0.1%~0.5% coupling agent and 0~20% linear low density polyethylene.
2. a kind of infiltration type degradable film according to claim 1, it is characterised in that: the coupling agent is vinyl front three
Oxysilane, methyltrimethoxysilane, triethanolamine borate, four n-propyl zirconates, distearyl acyl-oxygen aluminum isopropoxide
One of acid esters and aminopropyl triethoxysilane and its more than.
3. a kind of environment degradable courier bag thin-film material according to claim 1, it is characterised in that: the degradation of promoter is
In copper compound, iron compound, titanium compound, cerium compound, cobalt compound, lanthanum compound and praseodymium compound it is a kind of and its with
On.
4. a kind of environment degradable courier bag thin-film material according to claim 1, it is characterised in that: when the courier bag of production is thick
When degree is 30 microns, the mixture of starch and talcum powder is crossed to the sieve of 600 mesh, tailing over is 0~10%, by screenings after 800
Purpose sieve, tailing over is 5%~30%；
When the courier bag of production is with a thickness of 40 microns, the mixture of starch and talcum powder crosses 400 sieve, tail over as 0~
10%, by screenings after the sieve of 500 mesh, tailing over is 5%~30%；
When the courier bag of production is with a thickness of 50 microns, the mixture of starch and talcum powder is crossed into 325 mesh sieve, tail over as 0~
10%, by screenings after the sieve of 400 mesh, tailing over is 5%~30%.
5. the preparation method of environment degradable courier bag thin-film material, feature described in a kind of any one of Claims 1 to 4 exist
In: load weighted starch, talcum powder and degradation of promoter are put into heating stirring machine and are stirred, stirs 3~4min, then will
Polylactic acid, hexane diacid-terephthalic acid-butylene terephthalate copolymer, coupling agent and linear low density polyethylene are put into heating stirring
It is mixed in machine, degradable material is made using twin-screw extruder pelletizer in 6 ~ 8min of mixing time；
10 parts of degradable materials, 85 parts of linear low density polyethylene and 5 parts of White color masterbatches are mixed, it is mechanical to be put into three-layer co-extruded blown film
In the hopper of interior outer layer extruder；
In the hopper for the middle layer extruder that 100 parts of degradable materials are put into three-layer co-extruded blown film machinery；
10 parts of degradable materials, 85 parts of linear low density polyethylene and 5 parts of black color masterbatch are mixed, it is mechanical to be put into three-layer co-extruded blown film
In the hopper of interior inner layer extruder；Three extruders squeeze out simultaneously, and every layer of extrusion output is identical, by film head, blow molding, at
For courier bag thin-film material.
6. preparation method according to claim 5, it is characterised in that: the revolving speed of heating stirring machine is 500 ~ 600rpm, is stirred
Mixing temperature is 50 DEG C ~ 60 DEG C.
7. preparation method according to claim 5, it is characterised in that: the screw slenderness ratio L/D of twin-screw extruder pelletizer
It is 40 ~ 50, pelletization stage temperature is 155 DEG C ~ 185 DEG C.
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| CN119060423A (en) * | 2024-11-04 | 2024-12-03 | 天津包钢稀土研究院有限责任公司 | A puncture-resistant rubber product containing rare earth filler and preparation method thereof |
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Application publication date: 20190212 |