CN106279876A - A kind of nano montmorillonite modified high barrier property polyethylene coating materials and preparation method thereof - Google Patents
A kind of nano montmorillonite modified high barrier property polyethylene coating materials and preparation method thereof Download PDFInfo
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- CN106279876A CN106279876A CN201610652156.7A CN201610652156A CN106279876A CN 106279876 A CN106279876 A CN 106279876A CN 201610652156 A CN201610652156 A CN 201610652156A CN 106279876 A CN106279876 A CN 106279876A
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- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2205/03—Polymer mixtures characterised by other features containing three 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The present invention discloses a kind of nano montmorillonite modified high barrier property polyethylene coating materials, it is made up of the raw material of following weight portion: Low Density Polyethylene 60 80 parts, nano modification poly (propylene carbonate) 15 25 parts, tealeaf residue 20 30 parts, beta-schardinger dextrin-16 24 parts, citric acid 8 12 parts, methine sodium phosphate 0.5 2 parts, Radix Notoginseng 58 parts, Flos Lonicerae 48 parts, ethyl acetate 20 30 parts, emulsifying agent T 80 13 parts, phthalic acid two (2 ethyl hexyl) ester 23 parts, accelerant CZ 0.5 1.5 parts, sodium hydroxide solution is appropriate, and distilled water is appropriate.The present invention is carried out inclusion by grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag add in toothpaste sheet film Radix Notoginseng, Flos Lonicerae extract, has safety and certain medicinal efficacy slow release effect, additionally has the barrier feature of excellent steam and gas.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of poly-second of nano montmorillonite modified high barrier
Alkene coating materials and preparation method thereof.
Background technology
What dentifrice tube packaging was currently mainly used is multiple tube packaging, and the feature of a highly significant of composite soft tube is
Its body material is composite sheet, and composite sheet is that the coating materials produced by multiple different materials by the way of compound is multiple
It is combined.Its production technology is flexible, as can also be combined by extrusion with dry type is compound, can be combined in flakes after printing
Material tubulation, it is also possible to carrying out printing tubulation after producing into sheet material；Draw materials extensively, can be polyolefin, polyamides for material
Amine, polyester, aluminium foil, paper etc., can be blown film, casting films, co-extrusion film, biaxial stretching film, vacuum for the type of coating materials
Aluminizer, coated film etc..This makes composite sheet all have the highest at aspects such as barrier property, physical and mechanical properties, outward appearances
Motility.
Sheet material is for the packaging of Flexible tube for toothpaste, and its content lotion of toothpaste is direct and the oral contact of human body.Therefore
Whether proper the selection of packaging material is, and direct relation the healthy of people.In the past few years, food-safety problem increasingly causes
The attention of people.From tripolycyanamide event several years ago, to plasticiser disturbance in recent years, then to New Zealand's poison milk powder case, nothing
Do not affect the nerve that people are fragile to food safety.For toothpaste sheet material, it is also possible to regard " directly contacting human body " as
A kind of packaging material, how to ensure that some additives in package stock will not react with the composition in mastic, Cheng Liao
Problem faced by firstly the need of.
For toothpaste sheet material, main material or polyethylene and the material such as polypropylene and aluminium foil, the most poly-second
The production of alkene material can add the chemical substances such as antioxidant, opening agent, slipping agent, and these materials are in the effect of lotion of toothpaste
Under (lotion of toothpaste be well a kind of " extracting substance "), can migrate to mastic from thin film, the change of paste properties may be caused
Change.Hao Xihai, Sun Miao et al. embed fourth with beta-schardinger dextrin-in " the clove oil microcapsule antibacterial packing film " literary composition delivered
Microcapsule anti-bacterial agent prepared by essential oil, adds to and prepares Antibiotic Membrane in polyvinyl alcohol, and to Microencapsulated Slow anti-microbial property
Detecting, polymer carries food preservative functional components, by slowly discharging in food transport and storing process
To antiseptic effect.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nano montmorillonite modified high barrier property polyethylene coating materials
And preparation method thereof.
A kind of nano montmorillonite modified high barrier property polyethylene coating materials, is made up of the raw material of following weight portion: low-density
Polyethylene 60-80 part, nano modification poly (propylene carbonate) 15-25 part, tealeaf residue 20-30 part, beta-schardinger dextrin-16-24 part, Fructus Citri Limoniae
Acid 8-12 part, methine sodium phosphate 0.5-2 part, Radix Notoginseng 5-8 part, Flos Lonicerae 4-8 part, ethyl acetate 20-30 part, emulsifying agent T-80
1-3 part, phthalic acid two (2-ethyl hexyl) ester 2-3 part, accelerant CZ 0.5-1.5 part, sodium hydroxide solution is appropriate, distillation
Water is appropriate；
Wherein, described nano modification poly (propylene carbonate) is prepared with poly (propylene carbonate) melt blending by nano imvite, its
The percentage by weight of middle nano imvite is 0.1-1%.
Specifically comprise the following steps that
(1) preparation of grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag:
1., by tealeaf residue drying and pulverize, crossing 80-100 mesh sieve, the Folium Camelliae sinensis ground-slag obtained is immersed in sodium hydroxide solution
0.5-2.5 hour, thoroughly wash with the distilled water of 60-70 DEG C afterwards, standby for being dried 18-25 hour in case in 70-90 DEG C；
2., the Folium Camelliae sinensis ground-slag after activation processing is immersed in the ternary being made up of beta-schardinger dextrin-, citric acid, methine sodium phosphate
In aqueous solution, after supersound process 10-30 minute, oil bath is heated to 80-110 DEG C and is sufficiently stirred at this temperature, and 2-4 is little in reaction
Time, filtering after having reacted, filtering residue is product, is washed at neutrality, 50-70 DEG C be dried 20-25 hour, obtains β-ring and sticks with paste
Essence grafting Folium Camelliae sinensis ground-slag；
(2) Radix Notoginseng, the preparation of Flos Lonicerae/Benexate Hydrochloride:
1., powder is dried and be ground into Radix Notoginseng, Flos Lonicerae, add ethyl acetate, hot reflux extraction 1-in the water-bath of 60-80 DEG C
3 hours, filtered while hot, united extraction liquid, add appropriate distilled water after cooling, in mixed liquor, add emulsifying agent T-80,
Homogenizing 15-30 minute under the conditions of 5000-8000 rev/min, obtains emulsion；
2., weigh a certain amount of distilled water, add the grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag that step (1) obtains, fully after infiltration,
Emulsifying emulsion completely is poured in beta-schardinger dextrin-solution, stirs inclusion 20-30 minute, stand 0.5-1.5 hour
After, sucking filtration, wash, be dried, obtain Radix Notoginseng, Flos Lonicerae/Benexate Hydrochloride；
(3) preparation of nano modification poly (propylene carbonate): after poly (propylene carbonate) granule and nano imvite mix homogeneously, logical
Cross double screw extruder and carry out extruding pelletization, obtain nano modification poly (propylene carbonate)；
(4) the poly-carbonic acid of nano modification prepared by the Radix Notoginseng step (2) prepared, Flos Lonicerae/Benexate Hydrochloride, step (3)
Sub-propyl ester puts in high-speed mixer with Low Density Polyethylene mixs homogeneously, and controls rotating speed and is 800-1000 rev/min, 80-130
DEG C mixing 20-30 minute after, add surplus stock, continue mixing 30-60 minute, by double screw extruder blending extrusion, warp
Pellet is obtained after water-cooled, pelletizing；
(5) pellet blowfilm shaping on inflation film manufacturing machine that step (4) is obtained.
Wherein, the concentration of described sodium hydroxide solution be mass fraction be 25%-30%.
The present invention compared with prior art has the advantage that
(1) Radix Notoginseng, Flos Lonicerae are additives common in lotion of toothpaste, not only give off a strong fragrance, stable, and have can subside a swelling and stop
Bitterly, effect of promoting blood circulation to remove blood stasis, add in polyethylene coating materials base material, can from toothpaste sheet film under the effect of lotion of toothpaste
Slowly migrate in mastic, safe to the human body nontoxic, and have certain medicinal efficacy.
(2) additionally the present invention uses grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag that Radix Notoginseng, Flos Lonicerae extract are carried out inclusion, protects
Hold the bactericidal antiphlogistic effect of Folium Camelliae sinensis ground-slag, improved the bioavailability of tealeaf residue, additionally Radix Notoginseng, Flos Lonicerae are also had slow release
Effect, the polyethylene coating materials of preparation has the feature such as low cost, pollution-free, the splendid feature of environmental protection.
(3) the nano montmorillonite modified poly (propylene carbonate) that the present invention adds has higher barrier property, so that
The polyethylene coating materials of preparation has the barrier of excellent steam and gas, preferable oxygen barrier and water preventing ability.
Detailed description of the invention
A kind of nano montmorillonite modified high barrier property polyethylene coating materials, is made up of the raw material of following weight portion (kilogram):
Low Density Polyethylene 70, nano modification poly (propylene carbonate) 20, tealeaf residue 25, beta-schardinger dextrin-20, citric acid 10, methine phosphorus
Acid sodium 1, Radix Notoginseng 6, Flos Lonicerae 5, ethyl acetate 25, emulsifying agent T-80 2, phthalic acid two (2-ethyl hexyl) ester 2, accelerator
CZ 1, sodium hydroxide solution is appropriate, and distilled water is appropriate；
Wherein, described nano modification poly (propylene carbonate) is prepared with poly (propylene carbonate) melt blending by nano imvite, its
The percentage by weight of middle nano imvite is 0.8%.
Wherein, the concentration of described sodium hydroxide solution be mass fraction be 30%.
Specifically comprise the following steps that
(1) preparation of grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag:
1., by tealeaf residue drying and pulverize, crossing 100 mesh sieves, it is little that the Folium Camelliae sinensis ground-slag obtained is immersed in sodium hydroxide solution 2
Time, thoroughly wash with the distilled water of 65 DEG C afterwards, standby for being dried 20 hours in case in 80 DEG C；
2., the Folium Camelliae sinensis ground-slag after activation processing is immersed in the ternary being made up of beta-schardinger dextrin-, citric acid, methine sodium phosphate
In aqueous solution, supersound process is after 20 minutes, and oil bath is heated to 90 DEG C and is sufficiently stirred at this temperature, reacts 3 hours, has reacted
Filtering after one-tenth, filtering residue is product, is washed to neutrality, is dried 22 hours, obtains grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag at 60 DEG C；
(2) Radix Notoginseng, the preparation of Flos Lonicerae/Benexate Hydrochloride:
1., by Radix Notoginseng, Flos Lonicerae drying and be ground into powder, add ethyl acetate, in the water-bath of 70 DEG C, to extract 2 little in hot reflux
Time, filtered while hot, united extraction liquid, add appropriate distilled water after cooling, in mixed liquor, add emulsifying agent T-80,7000
Under the conditions of rev/min, homogenizing 20 minutes, obtain emulsion；
2., weigh a certain amount of distilled water, add the grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag that step (1) obtains, fully after infiltration,
Emulsifying emulsion completely is poured in beta-schardinger dextrin-solution, stirring inclusion 25 minutes, after standing 1 hour, sucking filtration, water
Wash, be dried, obtain Radix Notoginseng, Flos Lonicerae/Benexate Hydrochloride；
(3) preparation of nano modification poly (propylene carbonate): after poly (propylene carbonate) granule and nano imvite mix homogeneously, logical
Cross double screw extruder and carry out extruding pelletization, obtain nano modification poly (propylene carbonate)；
(4) the poly-carbonic acid of nano modification prepared by the Radix Notoginseng step (2) prepared, Flos Lonicerae/Benexate Hydrochloride, step (3)
Sub-propyl ester puts in high-speed mixer with Low Density Polyethylene mixs homogeneously, and controlling rotating speed is 900 revs/min, 90 DEG C of mixing 25
After minute, add surplus stock, continue mixing 40 minutes, by double screw extruder blending extrusion, obtain after water cooled, pelletizing
Pellet；
(5) pellet blowfilm shaping on inflation film manufacturing machine that step (4) is obtained.
Performance data after tested: hot strength (MPa): MD:89, TD:98；Tension fracture elongation rate (%): MD:186, TD:
82；Puncture strength (N): 5.3.
Claims (3)
1. a nano montmorillonite modified high barrier property polyethylene coating materials, it is characterised in that by the raw material group of following weight portion
Become: Low Density Polyethylene 60-80 part, nano modification poly (propylene carbonate) 15-25 part, tealeaf residue 20-30 part, beta-schardinger dextrin-16-
24 parts, citric acid 8-12 part, methine sodium phosphate 0.5-2 part, Radix Notoginseng 5-8 part, Flos Lonicerae 4-8 part, ethyl acetate 20-30 part,
Emulsifying agent T-80 1-3 part, phthalic acid two (2-ethyl hexyl) ester 2-3 part, accelerant CZ 0.5-1.5 part, sodium hydroxide is molten
Liquid is appropriate, and distilled water is appropriate；
Wherein, described nano modification poly (propylene carbonate) is prepared with poly (propylene carbonate) melt blending by nano imvite, its
The percentage by weight of middle nano imvite is 0.1-1%.
2. according to the preparation method of a kind of nano montmorillonite modified high barrier property polyethylene coating materials described in claims 1,
It is characterized in that, specifically comprise the following steps that
(1) preparation of grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag:
1., by tealeaf residue drying and pulverize, crossing 80-100 mesh sieve, the Folium Camelliae sinensis ground-slag obtained is immersed in sodium hydroxide solution
0.5-2.5 hour, thoroughly wash with the distilled water of 60-70 DEG C afterwards, standby for being dried 18-25 hour in case in 70-90 DEG C；
2., the Folium Camelliae sinensis ground-slag after activation processing is immersed in the ternary being made up of beta-schardinger dextrin-, citric acid, methine sodium phosphate
In aqueous solution, after supersound process 10-30 minute, oil bath is heated to 80-110 DEG C and is sufficiently stirred at this temperature, and 2-4 is little in reaction
Time, filtering after having reacted, filtering residue is product, is washed at neutrality, 50-70 DEG C be dried 20-25 hour, obtains β-ring and sticks with paste
Essence grafting Folium Camelliae sinensis ground-slag；
(2) Radix Notoginseng, the preparation of Flos Lonicerae/Benexate Hydrochloride:
1., powder is dried and be ground into Radix Notoginseng, Flos Lonicerae, add ethyl acetate, hot reflux extraction 1-in the water-bath of 60-80 DEG C
3 hours, filtered while hot, united extraction liquid, add appropriate distilled water after cooling, in mixed liquor, add emulsifying agent T-80,
Homogenizing 15-30 minute under the conditions of 5000-8000 rev/min, obtains emulsion；
2., weigh a certain amount of distilled water, add the grafted by beta cyclodextrin Folium Camelliae sinensis ground-slag that step (1) obtains, fully after infiltration,
Emulsifying emulsion completely is poured in beta-schardinger dextrin-solution, stirs inclusion 20-30 minute, stand 0.5-1.5 hour
After, sucking filtration, wash, be dried, obtain Radix Notoginseng, Flos Lonicerae/Benexate Hydrochloride；
(3) preparation of nano modification poly (propylene carbonate): after poly (propylene carbonate) granule and nano imvite mix homogeneously, logical
Cross double screw extruder and carry out extruding pelletization, obtain nano modification poly (propylene carbonate)；
(4) the poly-carbonic acid of nano modification prepared by the Radix Notoginseng step (2) prepared, Flos Lonicerae/Benexate Hydrochloride, step (3)
Sub-propyl ester puts in high-speed mixer with Low Density Polyethylene mixs homogeneously, and controls rotating speed and is 800-1000 rev/min, 80-130
DEG C mixing 20-30 minute after, add surplus stock, continue mixing 30-60 minute, by double screw extruder blending extrusion, warp
Pellet is obtained after water-cooled, pelletizing；
(5) pellet blowfilm shaping on inflation film manufacturing machine that step (4) is obtained.
3. according to the preparation side of a kind of nano montmorillonite modified high barrier property polyethylene coating materials described in claims 1,2
Method, it is characterised in that the concentration of described sodium hydroxide solution be mass fraction be 25%-30%.
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| CN201610652156.7A CN106279876A (en) | 2016-08-11 | 2016-08-11 | A kind of nano montmorillonite modified high barrier property polyethylene coating materials and preparation method thereof |
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| CN201610652156.7A CN106279876A (en) | 2016-08-11 | 2016-08-11 | A kind of nano montmorillonite modified high barrier property polyethylene coating materials and preparation method thereof |
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| CN201610652156.7A Withdrawn CN106279876A (en) | 2016-08-11 | 2016-08-11 | A kind of nano montmorillonite modified high barrier property polyethylene coating materials and preparation method thereof |
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Application publication date: 20170104 |